Glycoside derivatives, polymers containing glycoside derivatives, process for their preparation, and use of said polymers

ABSTRACT

The present invention provides a glycoside derivative represented by the formula ##STR1## wherein G--O-- is a saccharide residue having no protective group, R is a hydrogen atom or a methyl group, m is 1 or 2, n is an integer of 1 to 4, and l is an integer of 1 or more provided that l≦n; a polymer containing the glycoside derivative; a process for their preparation, and the use of the polymers.

This is a division of application Ser. No. 07/499,459 filed Jun 26,1990, which is now pending.

1. Field of the Invention

The present invention relates to glycoside derivatives, polymerscontaining the glycoside derivatives, a process for their preparationand the use of said polymers.

2. Prior Art

Polymers having saccharide residues at side chains are increasingly usedfor various applications utilizing their hydrophilic property andcompatibility with organisms, for example, as medical materialsincluding those compatible with blood, surface-treating agents, etc.

The heretofore proposed polymers having saccharide residues at sidechains are generally classified into the following two types.

(i) Polymers having saccharide residues obtained by the reaction ofknown polymers with sugar derivatives.

For example, Japanese Unexamined Patent Publications No. 106802/1985 andNo. 192704/1985 disclose the preparation of such polymers by reacting ahydroxymethylated polystyrene with a sugar having hydroxyl groupsprotected with protective groups such as acetyl groups, halogen atoms orthe like, followed by saponification of protective groups of the sugarwith an alkali. These polymers, however, have a poor hydrophilicproperty and a low compatibility with organisms because the protectivegroups on saccharide residues are not completely removed and thesaccharide residues are not uniformly added to the polymers. Furtherthis process can not regulate as desired the amount of the sugar to beadded and entails difficulties in removing the reagent used andpurifying the polymer thus formed.

(ii) Polymers formed by reacting a vinyl monomer with a saccharidehaving hydroxyl groups protected with protective groups such as acetylgroups, isopropylidene groups or the like and removing the protectivegroups after polymerization

For example, U.S. Pat. No. 3,225,012 discloses a polymer represented bythe formula ##STR2## the polymer being one prepared by polymerizing 1,2:5,6-di-O-isopropylidene-3-O-methacryloy-D-glucose and removing theisopropylidene groups from the glucose by acid hydrolysis.

U.S. Pat. No. 3,356,652 describes a polymer having structural unitsrepresented by the formula ##STR3##

As further example, Japanese Examined Patent Publication No. 42641/1982discloses a homopolymer represented by the formula ##STR4## wherein R isa hydrogen atom or a methyl group, R' is a sugar residue attached withthe acyl linkage at the 1- position and n is 10 to 1000, the homopolymerbeing one formed from a monomer which is a sugar derivative having amonosaccharide or disaccharide and an acrylate or methacrylate directlyattached to each other with the glycoside linkage.

These publications set forth techniques intended to remove theprotective groups with an alkali or acid from the hydroxyl groups of thesugar in the obtained polymer. However, the currently available art cannot completely remove the protective groups in polymers. Actually U.S.Pat. No. 3,356,652 teaches that it is impossible to completely removethe acetyl groups in a copolymer containing a hydrophobic monomer. Thusthe obtained polymer contains a substantial number of protected hydroxylgroups and is unsatisfactory in hydrophilic property and compatibilitywith organisms. The treatment of polymers with an alkali or acid impairsthe properties of the resulting polymer. Moreover such methodsnecessitate the neutralization of alkali or acid after removal ofprotective groups from hydroxyl groups and the washing by water of thesalt resulting from neutralization for elimination. The removal ofprotective groups renders the polymer hydrophilic to give an aqueousviscous solution or water-swollen gel, resulting in incompleteneutralization and desalting. Consequently the polymers formed by themethods are not suitable for use as medical materials.

As described above, polymers with saccharide residues at side chainshaving no protective group have not been heretofore obtained.

DISCLOSURE OF THE INVENTION

It is an object of the present invention to provide a monomeric compounduseful for synthesis of a polymer having as side chains saccharideresidues free of the protective group and a process for preparing thesame.

It is another object of the invention to provide a polymer having asside chains saccharide residues free of the protective group and aprocess for preparing the same.

According to the invention, there are provided glycoside derivatives, apolymer containing said glycoside derivatives and a process for theirpreparation, as described below.

(1) A glycoside derivative represented by the formula ##STR5## whereinG--O-- is a sugar residue free of the protective group, R is a hydrogenatom or a methyl group, m is 1 or 2, n is an integer of 1 to 4, and l isan integer of 1 or more provided that l ≦ n.

The glycoside derivative (1) is a novel compound undisclosed inliterature and useful as a monomer for synthesis of a polymer with sugarresidues at side chains having no protective group.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the IR spectrum of galactosyloxyethyl acrylate.

FIG. 2 shows the ¹ H-NMR spectrum of galactosyloxyethyl acrylate.

FIG. 3 shows the IR spectrum of galactosylethyl methacrylate.

FIG. 4 shows the ¹ H-NMR spectrum of galactosyloxyethyl methacrylate.

FIG. 5 shows the IR spectrum of glucosyloxypropyl methacrylate.

FIG. 6 shows the IR spectrum of glucosyloxyethyl acrylate.

FIG. 7 shows the ¹³ C-NMR spectrum of poly(glucosyloxyethylmethacrylate).

FIG. 8 shows the ¹ H-NMR spectrum of poly(glucosyloxyethylmethacrylate).

FIG. 9 shows the apparatus to check the specimens for the Non-foggingand drip-proof-properties. The reference characters designate: 1. aspecimen; 2. a stirring rod (blade); 3. thermometer; 4. a cover; 5.heat-insulating vessel; 6. heater; 7. warm water (40° C.); and 8. steam.

The glycoside derivative (1) is a novel compound undisclosed inliterature and useful as a monomer for synthesis of a polymer with sugarresidues at side chains having no protective group.

(2) A polymer containing a glycoside derivative, the polymer having atleast one of the following repeated units (I) represented by the formula##STR6## wherein G--O--, R, m, n, and l are as defined above.

The polymer (2) containing the glycoside derivative is a novel polymerundisclosed in literature. In the polymer, the sugar residues free ofthe protective group, namely having hydroxyl groups all remaining free,are attached to the main chain with the glycoside linkage. Sinceglycoside linkages exist in organisms or in nature, the foregoingpolymer is compatible with organisms. Further, because the hydroxylgroups of sugar residues in the polymer are unprotected and free, thepolymer is excellent in the hydrophilic property and compatibility withblood. The polymer has another advantage of high moldability. With thesecharacteristics, the polymer finds various applications asblood-compatible materials or like medical materials, coating materialsfor forming a non-fogging film on a transparent material such asplastics, glass or the like, water-absorbing resin materials, etc.

The term "saccharide residue" used herein refers to a saccharide residuewherein a hydrogen atom is removed from the hydroxyl group attached tothe anomeric carbon atom of saccharide. More specifically they are thesaccharide residues of monosaccharide or oligosaccharide having about 1to about 10, preferably about 1 to about 5, more preferably about 1 to3, sugar units. Examples of typical monosaccharides are glucose,mannose, galactose, glucosamine, mannosamine, galactosamine and likehexoses, arabinose, xylose, ribose and like pentoses, etc. Examples ofspecific oligosaccharides are maltose, lactose, trehalose, cellobiose,isomaltose, gentiobiose, melibiose, laminaribiose, chitobiose,xylobiose, mannobiose, sophorose and like disaccharides, maltotriose,isomaltotriose, maltotetraose, maltopentaose, mannotriose,manninotriose, etc.

The term "lower alkyl group" used herein is intended to denote astraight or branched chain alkyl group having about 1 to about 4 carbonatoms such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl,isobutyl, etc.

The glycoside derivative (1) of the present invention can be prepared byreacting an alkyl glycoside represented by the formula

    G--O--R.sup.1                                              (3)

wherein G--O-- is as defined above and R¹ is a lower alkyl group with anacrylate or methacrylate represented by the formula ##STR7## wherein R,m, n and l are as defined above in the presence of a heteropoly acid anda polymerization inhibitor. The reaction can be conducted in the absenceor the presence of a solvent.

The alkyl glycosides of the formula (3) useful as the starting compoundare not specifically limited and include those prepared by conventionalmethods such as the Koenigs-Knorr method, the Fischer's alcoholysismethod, the method proposed by us (Japanese Unexamined PatentPublication No. 84637/1988, "Synthesis of Glycoside by Heteropoly acid,(1) Synthesis of O-Alkylglycoside" reported in the 56th Spring AnnualMeeting, 1988, Japan Chemical Society), etc. Commercially availableglycosides may be used in the invention. Among them, preferable arealkyl glycosides in which the alkyl moiety is a straight or branchedchain alkyl group having about 1 to about 6 carbon atoms, preferablyabout 1 to about 4 carbon atoms, such as methyl glucoside, methylβ-D-galactoside, methyl D-maltoside, methyl β-D-mannoside, methylβ-D-xyloside, methyl D-maltoside, methyl β-D-lactoside, ethyl glucoside,ethyl galactoside, ethyl mannoside, ethyl xyloside, propyl glucoside,isopropyl glucoside, butyl glucoside, butyl galactoside, butyl xyloside,butyl mannoside, etc. These alkyl glycosides of the formula (3) areusable singly or at least two of them can be used in mixture.

The other starting material, i.e. the acrylate or methacrylate of theformula (4), is not specifically limited and can be any of conventionalones including 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate,2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate,diethyleneglycol acrylate, diethyleneglycol methacrylate, glycerinacrylate, glycerin methacrylate, pentaerythritol acrylate,pentaerythritol methacrylate, etc.

The amount of the acrylate or methacrylate of the formula (4) used isnot specifically limited and is about 2 to about 10 moles, preferablyabout 4 to about 6 moles, per mole of the alkylglycoside of the formula(3).

The heteropoly acid is not specifically limited. Preferred heteropolyacids are phosphomolybdic acid, silicomolybdic acid, phosphotungsticacid, silicotungstic acid, etc. These heteropoly acids are useablesingly or at least two of them can be used in mixture. The amount of theheteropoly acid used is not specifically limited and is about 1 to about20% by weight, preferably about 5 to about 10% by weight, based on thealkyl glycoside of the formula (3) used.

The polymerization inhibitor is not specifically limited and can be anyof conventional ones. Examples of useful inhibitors are hydroquinonemonomethyl ether, hydroquinone monoethyl ether, butylhydroxytoluene,butylcatechol, benzoquinone, nitrobenzene, cupric chloride, ferricchloride, etc. These inhibitors are usable singly or at least two ofthem can be used in mixture. The amount of the inhibitor used is notspecifically limited, and is about 0.5 to about 5% by weight, preferablyabout 1 to about 2% by weight, based on the acrylate or methacrylate ofthe formula (4).

Useful solvents are those which affect the reaction in no way. Examplesof such solvents are halogenated hydrocarbons such as dichloromethane,chloroform, 1,2-dichloroethane, 1,1,1-trichloroethane,1,1,2-trichloroethane, 1,1,2,2-tetrachloroethane, chlorobenzene and thelike; aromatic hydrocarbons such as benzene, toluene, xylene and thelike; and ethers such as ethyl ether, isopropyl ether, ethyleneglycoldimethyl ether, ethyleneglycol diethyl ether, diethyleneglycol dimethylether, dioxane, tetrahydrofuran and the like. These solvents are usablesingly or at least two of them can be used in mixture.

The reaction temperature and the reaction time are not specificallylimited. The reaction temperature is in the range of about 50° to about150° C., preferably about 80° to about 120° C. The reaction time is inthe range of about 1 to 3 hours.

The glycoside derivative (1) can be prepared also by reacting a sugarhaving no protective group with an ester of acrylic or methacrylic acidin the presence of an acid catalyst and a polymerization inhibitor whilefeeding oxygen to the reaction system. This process gives thecontemplated glycoside derivative (1) in a high yield using an easilyavailable sugar having no protective group without use of an alkylglycoside which is relatively difficult to synthesize or obtain.

Among sugars having no protective group, monosaccharides oroligosaccharides having about 1 to about 10, preferably about 1 to about5, more preferably about 1 to about 3, sugar units as exemplified aboveare usable without specific limitation.

Esters of acrylic or methacrylic acids useful in the invention are thoseof the formula (4). The amount of such ester used is not specificallylimited but usually in the range of about 2 to about 20 moles,preferably about 4 to about 10 moles, per mole of the sugar having noprotective group.

The acid catalyst is not specifically limited and can be any ofconventional ones including inorganic acids such as sulfuric acid,chlorosulfonic acid, hydrochloric acid, hydrobromic acid, perchloricacid, nitric acid, phosphorus trichloride, phosphorus pentachloride,phosphorus oxychloride, stannic chloride, aluminum chloride, ironchloride, zinc chloride and the like, organosulfonic acids such astoluenesulfonic acid, laurylsulfonic acid, methanesulfonic acid,alkylbenzenesulfonic acid, trifluoromethanesulfonic acid and the like,and esters of sulfuric acids such as lauryl sulfate, methyl sulfate,ethyl sulfate and the like. Strongly acidic ion-exchange resins (acidtype), NAFION and like acidic polymers are also usable as the acidcatalyst. Preferred acid catalysts are those which can not be readilyreduced. The acid catalysts are usable singly or at least two of themcan be used in mixture. The amount of the acid catalyst used is notspecifically limited but usually in the range of about 0.001 to about2.0% by weight, preferably about 0.005 to about 0.1% by weight, based onthe ester of acrylic or methacrylic acid used.

The polymerization inhibitors as exemplified above can be used in thisreaction and the amount of the inhibitor is approximately the same asdescribed above.

The methods for feed of oxygen to the reaction system are notspecifically limited. The feed of oxygen may be carried out, forexample, by blowing oxygen or an oxygen-containing gas such as air intothe reaction mixture. The amount of oxygen to be blown is notspecifically limited and can be suitably determined according to theprogress of the reaction. For example, about 30 to about 60 1/h ofoxygen is fed to about 40 to about 50 1 of the total reaction mixture.

The above reaction is conducted usually in the absence of a solvent at atemperature of about 80° to about 130° C., preferably about 100° toabout 120° C. and is completed in about 2 to about 5 hours. It ispreferred to conduct the reaction with stirring because the reactionmore advantageously proceeds with an increase in the area of contactbetween the reaction mixture and oxygen.

The glycoside derivative (1) prepared by the above reaction can bepurified by common purification methods such as silica gelchromatography, extraction or the like.

The polymer 2) of the invention includes homopolymers having therepeated units (I), copolymers having at least two different repeatedunits (I) and copolymers having the repeated units (I) and repeatedunits copolymerizable therewith. Olefin-type repeated units are usableas the copolymerizable units. More specific examples thereof arerepeated units represented by the formula (II) ##STR8## wherein R², R³and R⁴ are the same or different and each represent a hydrogen atom or alower alkyl group, and R⁵ is a group ##STR9## (wherein R⁶ is a hydrogenatom, an alkyl group, a hydroxyalkyl group, a cycloalkyl group, anaminoalkyl group, a dialkylaminoalkyl group, a glycidyl group, atetrahydrofuranyl group, a benzyl group, a group --(CH₂ CH₂ O)_(a) CH₂CH₂ OH (wherein a is an integer of 1 to 10), a group ##STR10## (whereinR⁷ is a hydrogen atom or a lower alkyl group, provided that two groupsR⁷ are the same or different), a cyano group, a hydroxy group, a group##STR11## (wherein R⁸ is a lower alkyl group), a phenyl group which mayhave at least one substituent selected from the group consisting ofchlorine atom, lower alkyl group, cyano group, amino group, hydroxygroup and lower alkoxy group, a pyridyl group optionally substitutedwith a lower alkyl group, a 2-oxopyrrolyl group optionally substitutedwith an alkyl group, or a carbazole group.

Examples of the alkyl group represented by R⁶ in the formula (II) arestraight chain or branched chain alkyl groups having about 1 to about 22carbon atoms, preferably about 1 to about 10 carbon atoms such asmethyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, pentyl,hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl,tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl,eicosyl and the like.

Examples of the hydroxyalkyl group are hydroxyalkyl groups in which thealkyl moiety is a straight chain or branched chain alkyl group having 1to 5 carbon atoms, such hydroxyalkyl groups including, for example,hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl,4-hydroxybutyl, 3-hydroxybutyl, 2-methyl-3-hydroxypropyl,5-hydroxypentyl, 4-hydroxypentyl, 2-methyl-4-hydroxybutyl,2-methyl-5-hydroxypentyl, 2-methyl-4-hydroxypentyl, etc.

Examples of the cycloalkyl group are cycloalkyl groups having 3 to 8carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cycloheptyl, cyclooctyl, etc.

Examples of the aminoalkyl group are aminoalkyl groups in which thealkyl moiety is a straight chain or branched chain alkyl group having 1to 5 carbon atoms such as aminomethyl, aminoethyl, 2-aminoethyl,aminopropyl, aminobutyl, aminopentyl and the like.

Examples of the dialkylaminoalkyl group are dialkylaminoalkyl groupswherein the aminoalkyl moiety is a straight chain or branched chainaminoalkyl group having 1 to 6 carbon atoms and substituted on thenitrogen atom with 2 straight chain or branched chain alkyl groupshaving about 1 to about 4 carbon atoms such as dimethylaminomethyl,diethyl-aminomethyl, 2-dimethylaminoethyl, 2-diethylaminoethyl,dimethylaminopropyl, diethylaminopropyl, dimethylaminobutyl,diethylaminobutyl, dimethylaminopentyl, diethylaminopentyl and the like.

Examples of the pyridyl group represented by R⁵ and optionallysubstituted with a lower alkyl group are 2-pyridyl, 3-pyridyl,4-pyridyl, 1-methyl-4-pyridyl, etc.

The polymer (2) of the invention can be prepared by polymerizing atleast one of glycoside derivatives (1), or a combination of thederivative (1) and a compound copolymerizable therewith. This processeliminates the need for protecting the hydroxyl groups of the sugar andthus can produce with extreme ease a polymer wherein the saccharideresidues having no protective group are attached as side chains. Theprocess can produce a polymer having the contemplated properties becausethe sugar content of the polymer can be regulated as desired. Since anacid or alkali need not be used in the process, the resulting polymercan be easily purified and can be used as it is for applications as amedical material or the like.

Usable as compounds copolymerizable with the glycoside derivative (1)are olefin-type compounds represented by the formula ##STR12## whereinR², R³, R⁴ and R⁵ are as defined above. Examples of such compounds areas follows.

(i) Hydrophobic olefin-type compounds including alkyl esters of acrylicor methacrylic acids such as methyl methacrylate, methyl acrylate, ethylmethacrylate, ethyl acrylate, butyl methacrylate, butyl acrylate, amylmethacrylate, amyl acrylate, hexyl methacrylate, hexyl acrylate, octylmethacrylate, octyl acrylate, decyl methacrylate, decyl acrylate,undecyl methacrylate, undecyl acrylate, lauryl methacrylate, laurylacrylate, stearyl methacrylate, stearyl acrylate, cycloalkyl esters ofacrylic or methacrylic acids such as cyclopentyl acrylate ormethacrylate, cyclohexyl acrylate or methacrylate, other vinyl compoundssuch as styrene, vinyl acetate, vinyl propionate, nitriles such asacrylonitrile, etc.

(ii) Hydrophilic olefin-type compounds such as 2-hydroxyethylmethacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate,2-dimethylaminoethyl acrylate or methacrylate, 2-diethylaminoethyl,acrylate or methacrylate, 3-dimethylaminopropyl acrylate ormethacrylate, 3-diethylaminopropyl acrylate or methacrylate,polyethylene glycol monoacrylate or monomethacrylate, acrylamide,methacrylamide, dimethylacrylamide, dimethylmethacrylamide, acrylicacid, methacrylic acid, N-vinylpyrrolidone, vinyl carbazole and thelike.

(iii) Polyfunctional olefin-type compounds such as ethylene glycoldiacrylate or dimethacrylate, diethylene glycol diacrylate ordimethacrylate, triethylene glycol diacrylate or dimethacrylate, vinylacrylate or methacrylate, allyl acrylate or methacrylate,divinylbenzene, diallylphthalate, trimethylolpropane triacrylate ortrimethacrylate and the like.

The polymerization reaction can be conducted by conventional methodssuch as mass polymerization, solution (or homogeneous) polymerization,suspension polymerization, emulsion polymerization, radiationpolymerization (using γ ray, electron beam or the like) or the like.

For example, solution polymerization is performed in a solvent in thepresence or the absence of a polymerization initiator. Useful initiatorsare not specifically limited insofar as they are soluble in a solvent.Examples of such initiators are organic solvent-soluble initiators suchas benzoyl peroxide, azobisisobutyronitrile (AIBN), di-tertiary butylperoxide and the like, water-soluble initiators such as ammoniumpersulfate (APS), potassium persulfate and the like, redox-typeinitiators which are combinations of such initiator and Fe²⁺ salt,sodium hydrogensulfite or like reducing agent, etc. Solvents for use inpolymerization of at least one glycoside derivative (1) are notspecifically limited insofar as they can dissolve the polymers. Examplesof such solvents are water, dimethylsulfoxide (DMSO), dimethylformamide(DMF), formamide, a solvent mixture of a least two of them, etc. Incopolymerization of the glycoside derivative (1) and a compoundcopolymerizable therewith, the solvent to be used is suitably selectedaccording to the solubility of the resulting copolymer from, e.g. DMSO,water-containing polar solvents (methanol, isopropanol, acetone, ethylcellosolve, etc., the water content being determined according to thesolubility of the copolymer), etc. A solvent having a low chain transferconstant, such as DMSO or the like, is preferably used in preparation ofa high-molecular weight polymer, whereas a solvent having a high chaintransfer constant, such as isopropanol or the like, is desirable inpreparation of a low-molecular weight polymer.

There is no specific restriction on the mixing ratio of the monomercomponent, polymerization initiator and solvent to be used in theinvention. Preferable to use are less than about 5 parts by weight ofthe polymerization initiator and an excess amount, preferably about 200to about 2000 parts by weight, of the solvent, per 100 parts of themonomer component.

In copolymerization of at least two different glycoside derivatives (1),the mixing ratio thereof is not specifically limited. Incopolymerization of the glycoside derivative (1) and a compoundcopolymerizable therewith, the mixing ratio thereof is not specificallyrestricted and can be suitably selected according to the use of theresulting copolymer. In this case it is preferred to use about 1 toabout 99% by weight, preferably about 5 to about 95% by weight, of theformer.

The polymerization reaction is preferably conducted in the absence ofoxygen. Oxygen can be removed from the reaction system as by usualatmosphere-replacing means such as degassing, nitrogen replacement orthe like. The reaction is carried out at about 10° to about 200° C.,preferably about 30° to about 120° C. and is completed in about 0.5 toabout 48 hours, preferably about 2 to about 20 hours.

Suspension polymerization and emulsion polymerization can be conductedin the same manner as solution polymerization.

Mass polymerization method is suited for preparation of a copolymer fromthe glycoside derivative (1) and an olefin-type compound (5) since theglycoside derivative (1) is soluble in most of the foregoing olefin-typecompounds (5). The mass polymerization reaction is effected in thepresence or the absence of a polymerization initiator. The initiators asexemplified hereinbefore can be used. The reaction conditions are thesame as those for solution polymerization.

After completion of polymerization, the polymer of the invention can beseparated or collected from the reaction product and purified by usualmethods, for example collected by admixing the reaction product with apoor solvent to precipitate the polymer. In preparation of a homopolymerof the glycoside derivative (1) or a copolymer of at least two differentglycoside derivatives (1), methanol, ethanol, acetone or the like can beused as a poor solvent. In preparation of a copolymer of the glycosidederivative (1) and a compound copolymerizable therewith, a solvent issuitably selected since the solubility varies with the composition ofcomponents to be polymerized. The collected polymer may be furtherpurified by, for example, reprecipitation or the like.

The thus obtained polymer of the invention has a molecular weightranging from hundreds to thousands. The intrinsic viscosity [η] (inDMSO, 25° C.) of the polymer is variable over a wide range of about 0.03to about 100 depending on the polymerization degree, the kind ofcomponents used for polymerization and the like, for example about 0.03to about 40, preferably about 0.1 to about 10 in case of thepolymerization degree of about 50 to about 10000 or one to threecomponents used.

The copolymer of the glycoside derivative (1) and a compoundcopolymerizable therewith has about 1 to about 99 mole %, preferablyabout 1 to about 95 mole %, more preferably about 5 to about 90 mole %,of repeated units (I).

The polymer of the invention is excellent in the film forming propertyand thus can be molded into a film, a sheet or the like by flow of thereaction product as it is on completion of the reaction.

Among the polymers of the invention, a water-soluble or water-swellingone can be rendered insoluble in water by crosslinking the hydroxylgroups of the sugar residues.

The hydroxyl groups can be crosslinked, for example, with an acidcatalyst. Stated more specifically, the polymer of the invention isdissolved in a suitable solvent, an acid catalyst is added to thesolution and the mixture is heated. Useful acid catalysts are notspecifically limited and include p-toluenesulfonic acid, hydrochloricacid, sulfuric acid, ammonium chloride and the like. The amount of theacid catalyst used is about 0.01 to about 5 parts by weight, preferablyabout 0.05 to about 2 parts by weight, per 100 parts of the polymer ofthe invention. The solvent is suitably selected from the solventsexemplified above for polymerization. The crosslinking reaction isconducted at a temperature of about 70° to about 180° C., preferablyabout 80 to about 150° C. and is completed in about 1 to about 90minutes, preferably about 5 to about 60 minutes. After completion of thereaction, the catalyst can be easily removed from the reaction system byusual methods, as by immersion of the reaction mixture in water,methanol, ethanol or the like for minutes to hours.

The hydroxyl groups can be also crosslinked with a crosslinking agent inthe presence of a catalyst. Stated more specifically a catalyst and acrosslinking agent are added to a solution of the polymer of theinvention and the mixture is heated. Examples of useful crosslinkingagents are formalin, melamine-formaldehyde adduct, urea-formaldehydeadduct and like formalin-type crosslinking agents, methylol-typecrosslinking agents, epichlorohydrin, glycidol, polyfunctional epoxycompounds (sorbitol polyglycidyl ether and the like) and like epoxy-typecrosslinking agent or a methylol-type crosslinking agent, the same acidas above can be used as a catalyst. In using an epoxy-type crosslinkingagent, common curing catalysts for epoxy resins can be used whichinclude, for example, boron trifluoride, tin tetrachloride, lithiumhydroxide, tri-n-butrylamine, triethylamine, etc. Whichever crosslinkingagent may be used, the amount of the catalyst used, type of solvent,reaction temperature, and reaction time are the same as in the foregoingcrosslinking reaction using an acid catalyst alone.

Another object of the invention is to provide use of the polymer (2) ofthe invention.

According to the invention, there is provided a material compatible withblood and containing the polymer (2) of the invention. The materials ofthe invention are significantly suitable for use with organisms, highlycompatible with blood, and effective in preventing thrombosis.

The materials of the invention are usable for substantially all medicalinstruments and materials to be contacted with blood or bloodcomponents, which include blood bypass tubes, column tubes forseparation of blood cells, blood bags, artificial organs, catheters,carriers for gradual release of medicaments, etc.

The materials of the invention have a high moldability and can be moldedinto medical instruments or materials in the desired shape. The moldingmethods for the materials of the invention are not specifically limited.The materials of the invention can be molded in the same manner as incommon molding of plastics.

The materials of the invention can be applied to the surface of existingmolded articles of nylon, polyvinyl chloride, polystyrene glass or thelike to form a coating film thereon. For application, the material ofthe invention is dissolved in a suitable solvent and the solution isapplied to an existing molded article by brushing, immersion or likecommon coating methods and dried. Solvents useful for dissolving thematerials of the invention can be suitably selected from the solventsexemplified above for polymerization. The solution of the material ofthe invention is applied in an amount not specifically limited butusually in the range sufficient to form a coating film of about 0.1 toabout 100 μm, preferably about 0.5 to about 50 μm in dry thickness. Thecoating thus applied is dried at a temperature of about 50° to about150° C., and may be subsequently vacuum dried when so required.

According to the invention, there is also provided a non-foggingdrip-proof composition containing the polymer (2) of the invention.

The composition of the invention has a high levels of non-foggingproperty, drip-proofness, abrasion resistance and weatherability and thecoating film of the compositions sustain these properties for a longterm.

The composition of the invention can achieve such remarkable results forreasons remaining unclear. presumably the reasons may be as follows. Theglycoside derivative-containing polymer (2) contains sugar residueshaving no protective group, namely sugar residues having hydroxyl groupsall remaining free and attached to the main chain with the glycosidiclinkage. The polymer of the invention contains a number of hydroxylgroups in the molecule and is marked in hydrophilic property, henceeffective in preventing fogging and dripping. Since the glycosidederivative in the polymer of the invention has relatively bulkymolecules, and the hydroxyl groups in the glycoside portion of theglycodise derivative partly crosslink on heating in forming a coatingfilm, the film is given improved abrasion resistance andweatherablility. Moreover, the polymer is prevented from oozing out fromthe coating film due to the bulkiness of saccharide residues andcrosslinking of hydroxyl groups, so that the properties of the film aresustained for a prolonged period.

The composition of the invention may contain a crosslinking agent aswell as the glycoside derivative-containing polymer (2) as the effectivecomponent. The added crosslinking agent causes the hydroxyl groups inthe polymer (2) to partly crosslink therewith and in case of copolymer,allows some of hydroxyl groups and/or the functional group of thecompound copolymerizable with the glycoside derivative to crosslinktherewith, whereby the physical properties of the film such as surfacehardness are improved while the hydrophilic property of the film issubstantially not reduced because most of the remaining hydroxyl groupsretain the hydrophilic property of the film.

There is no specific restriction on useful crosslinking agents insofaras they can crosslink the hydroxyl groups or functional groups of thecompound copolymerizable with the glycoside derivative (1). Examples ofuseful crosslinking agents are organic polyfunctional isocyanatecompounds, polyfunctional epoxy compounds, formalin, glycidol, melamine,silicone oligomer, etc. The amount of the crosslinking agent used issuitably selected over a wide range according to the amount of theglycoside derivation in the glycoside derivative-containing polymer. Forexample, in case of a homopolymer, the amount of the crosslinking agentused is about 3 to about 400 parts by weight, preferably about 30 toabout 200 parts by weight, per 100 parts by weight of the homopolymer.In case of a copolymer, the amount of the agent used is about 3 to about350 parts by weight, preferably about 5 to about 150 parts by weight,per 100 parts by weight of the copolymer.

The composition of the invention may further contains a curing catalyst,colloidal silica, silane coupling agent and the like to improve theabrasion resistance, weatherablility and other properties of the film.Examples of useful curing catalysts are p-toluenesulfonic acid,triethylamine, diazabicycloundecene, hydroxide of alkali metal,phosphine, dibutyltin dilaurate, etc. Examples of useful colloidalsilicas are ultrafine silica particles, ultrafine silica sols dispersedlike a colloid in a hydrophilic solvent, etc. Examples of usefulsilane-type coupling agents are γglycidoxypropyltrimethoxysilane,γ-methacryloyloxypropyltrimethoxysilane, etc. A surfactant or the likemay be added to the composition to improve the hydrophilic property ofthe film. The surfactant is not specifically limited and can be anionic,cationic or nonionic.

The composition of the invention can be prepared by dissolving ordispersing the polymer (2) of the invention and other components when sorequired in a suitable solvent. Examples of useful solvents are aromatichydrocarbons such as toluene, xylene and the like, saturatedhydrocarbons such as cyclohexane, n-hexane, octane and the like,alcohols such as methanol, ethanol, iso-propanol, butanol, iso-butanol,ethylene glycol monomethyl ether and the like, esters such as methylacetate, ethyl acetate and the like, amides such as DMF and the like,ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone,cyclohexanone and the like, water, etc. These solvents are usable singlyor at least two of them can be used in mixture. The concentration of theglycoside derivative-containing polymer in the composition of theinvention is suitably selected over a wide range without specificlimitation but usually in the range of about 2 to about 80% by weight,preferably about 5 to about 50% by weight, based on the wholecomposition.

A substrate of transparent material such as glass, plastics or the likecan be improved in the non-fogging property and drip-proofness byapplying the composition of the invention to the substrate to form acoating film. Stated more specifically, the composition of the inventionis applied to the surface of such substrate and cured to form a coatingfilm having non-fogging property and drip-proofness. The amount of thecomposition of the invention to be applied is not specifically limited,but is in a range sufficient to provide a cured film about 1 to about500 μm, preferably about 3 to about 100 μm in thickness. The compositionis cured usually at room temperature, or when required, may be cured byheating to a temperature of from higher than room temperature to about2000° C., preferably about 50° to about 200° C. To improve the adhesionbetween the substrate and the film, the substrate surface may besubjected to an activating gas treatment, sandblasted or chemicallytreated with an acid, base, oxidizing agent or the like, or a primercoating may be formed on the substrate.

The composition of the invention may be mixed with a transparentmaterial prior to molding.

The composition of the invention can be used for substantially all ofplastics, glass and articles of such materials, for example, goggles,plastics lenses, plastics containers and like plastics articles, glassbodies, glass lenses for spectacles and like glass articles.

EXAMPLES

The present invention will be described below in greater detail withreference to the following Examples.

Given below are Examples 1 to 34 illustrating the preparation ofglycoside derivatives (monomeric compounds).

EXAMPLE 1

A 19.4 g quantity of methyl glucoside (STA-MEG 106, product of HorizonChemical A. E. Staley Manufacturing Co.) was suspended in 140 ml of2-hydroxyethyl methacrylate. To the suspension were added 2.6 g ofhydroquinone monomethyl ether and 1.0 g of phosphomolybidic acid, andthe mixture was stirred well and gradually heated. After heating to atemperature of 80° to 90° C., the mixture was further stirred for about2 hours while maintaining the same temperature and was neutralized with2N sodium hydroxide. The obtained reaction mixture was concentratedunder reduced pressure and subjected to silica gel chromatography(eluent, chloroform:methanol=9:1). A fraction (R_(f) =0.2) of thereaction mixture was concentrated, giving 20.1 g of galactosyloxyethylacrylate (HEMA-Glc) as an oily product (yield 68.8%).

The analysis of the obtained compound gave the following results.

Silica gel TLC: 1 spot

Silica gel plate; product of Merck & Co., Inc., 60F254

Eluent; chloroform:methanol=4:1

Infrared absorption spectrum analysis (liquid film method, cm⁻¹):

FIG. 1 shows the IR spectrum of the above compound. Major peaks were asfollows. 3400 (broad absorption due to O--H stretching) 2940 (absorptiondue to C--H stretching) 1710 (absorption due to C═O, carbonyl group)1640 (absorption due to C═C, double bond) 1450 (absorption due todeformation vibrations of groups such as CH₂, CH₃ and the like) 1050(broad absorption indicated by a peak in a shape peculiar to sugarresidue)

¹ H-NMR: δ ppm (in D₂ O):

FIG. 2 shows the ¹ H-NMR spectrum of the above compound. Major peakswere as follows. 6.1, 5.6 (CH₂ ═) 4.9 (α-anomer hydrogen) 4.2-4.6(--OCH₂ --) 3.2-4.2 (sugar skeleton) 1.9 (CH₃).

    ______________________________________                                        Elementary analysis                                                                   C           H      O                                                  ______________________________________                                        Found     49.2%         7.0%   43.8%                                          Calcd.    49.3%         6.9%   4.38%                                          ______________________________________                                    

EXAMPLE 2

A 20.0 g quantity of methyl β-D-galactoside (product of Nacalai Co.,Ltd., a guaranteed reagent)was suspended in 150 ml of 2-hydroxyethylacrylate. To the suspension were added 1.0 g of butylhydroxytoluene and1.0 g of phosphomolybdic acid, and the mixture was stirred well andgradually heated. After heating to a temperature of 60° to 70° C., themixture was further stirred for about 2 hours while maintaining the sametemperature, and was neutralized with 2N sodium hydroxide. The obtainedreaction mixture was purified in the same manner as in Example 1. Afraction (R_(f) =0.2) of the reaction mixture was concentrated, giving15.8 g of galactosyloxyethylacrylate (HEA-Gal) as an oily product (yield55%).

The analysis of the obtained compound gave the following results.

Silica gel TLC: 1 spot

Silica gel plate; product of Merck & Co., Inc., 60F254

Eluent; chloroform:methanol=4:1

Infrared absorption spectrum analysis (liquid film method, cm⁻¹): 3400(broad absorption due to O--H stretching) 2940 (absorption due to C--Hstretching) 1710 (absorption due to C═O, carbonyl group) 1640(absorption due to C═C, double bond) 1450 (absorption due to deformationvibrations of CH₂ and the like) 1050 (broad absorption indicated by apeak in a shape peculiar to sugar residue)

¹ H-NMR: δ ppm (in D₂ O): 5.6-6.8 (CH₂ ═CH--) 4.9 (α-anomer hydrogen)4.2-4.5 (--OCH₂ --) 3.4-4.2 (sugar skeleton).

    ______________________________________                                        Elementary analysis                                                                   C           H      O                                                  ______________________________________                                        Found     47.3%         6.6%   46.1%                                          Calcd.    47.5%         6.5%   46.0%                                          ______________________________________                                    

EXAMPLE 3 TO 11

The desired compounds were prepared by the same procedure as in Example1 with the exception of using the following starting compounds andcatalysts.

EXAMPLE 3

Starting compounds:

    ______________________________________                                        Methyl β-D-galactoside                                                                           19.4   g                                              2-Hydroxyethyl methacrylate                                                                           140 ml                                                Catalyst: Silicotungstic acid                                                                         1.0 g                                                 ______________________________________                                    

Desired compound:

Galactosyloxyethyl methacrylate (HEMA-Gal)

Yield: 22.0 g (72%)

Infrared absorption spectrum analysis (liquid film method, cm⁻¹):

FIG. 3 shows the IR spectrum of the obtained compound. Major peaks wereas follows. 3400 (broad absorption due to O--H stretching) 2940(absorption due to C--H stretching) 1710 (absorption due to C═O,carbonyl group) 1640 (absorption due to C═C, double bond) 1450(absorption due to deformation vibrations of groups such as CH₂, CH₃ andthe like) 1050 (broad absorption indicated by a peak in a shape peculiarto sugar residue)

¹ H-NMR: δ ppm (in D₂ O):

FIG. 4 shows the ¹ H-NMR spectrum of the above compound. Major peakswere as follows. 6.1, 5.6: CH₂ ═; 4.9: α-anomer hydrogen; 4.2-4.5:--OCH₂ --; 3.2-4.2: sugar skeleton; 1.9: CH₃.

    ______________________________________                                        Elementary analysis                                                                   C           H      O                                                  ______________________________________                                        Found     49.0%         6.9%   44.1%                                          Calcd.    49.3%         6.9%   43.8%                                          ______________________________________                                    

EXAMPLE 4

Starting compounds:

    ______________________________________                                        Methyl β-D-mannoside                                                                              19.4   g                                             2-Hydroxyethyl methacrylate                                                                            140 ml                                               Catalyst: Phosphomolybdic acid                                                                         1.0 g                                                ______________________________________                                    

Desired compound:

Mannosyloxyethyl methacrylate (HEMA-Man)

Yield: 18.5 g (63%)

Infrared absorption spectrum analysis (liquid film method, cm⁻¹):

Silica gel plate; product of Merck & Co., Inc., 60F254

Eluent; chloroform:methanol=4:1

Infrared absorption spectrum analysis (liquid film method, cm⁻¹): 3400(broad absorption due to O--H stretching) 2940 (absorption due to C--Hstretching) 1710 (absorption due to C═O, carbonyl group) 1640(absorption due to C═C, double bond) 1450 (absorption due to deformationvibrations of groups such as CH₂, CH₃ and the like) 1050 (broadabsorption indicated by a peak in a shape peculiar to sugar residue)

¹ H-NMR: δ ppm (in D₂ O): 6.1, 5.6: CH₂ ═; 4.9: α-anomer hydrogen;4.2-4.5: --OCH₂ 13; 3.2-4.2: sugar skeleton; 1.9: CH₃.

    ______________________________________                                        Elementary analysis                                                                   C           H      O                                                  ______________________________________                                        Found     49.1%         7.0%   43.9%                                          Calcd.    49.3%         6.9%   43.8%                                          ______________________________________                                    

EXAMPLE 5

Starting compounds:

    ______________________________________                                        β-D-xyloside       16.4   g                                              2-Hydroxyethyl methacrylate                                                                           140 ml                                                Catalyst: Silicotungstic acid                                                                         1.0 g                                                 ______________________________________                                    

Desired compound:

Xylosyloxyethyl methacrylate (HEMA-Xyl)

Yield: 18.0 g (69%

Infrared absorption spectrum analysis (liquid film method, cm⁻¹): 3400(broad absorption due to O--H stretching) 2940 (absorption due to C--Hstretching) 1710 (absorption due to C═O, carbonyl group) 1640(absorption due to C═C, double bond) 1450 (absorption due to deformationvibrations of groups such as CH₂, CH₃ and the like) 1050 (broadabsorption indicated by a peak in a shape peculiar to sugar residue)

¹ H-NMR: δ ppm (in D₂ O): 6.1, 5.6: CH₂ ═; 4.9: α-anomer hydrogen;4.2-4.5: sugar skeleton; 1.9: CH₃.

    ______________________________________                                        Elementary analysis                                                                   C           H      O                                                  ______________________________________                                        Found     49.8%         6.9%   43.3%                                          Calcd.    50.3%         6.9%   42.7%                                          ______________________________________                                    

EXAMPLE 6

Starting compounds:

    ______________________________________                                        Methyl glucoside         19.4   g                                             2-Hydroxypropyl methacrylate                                                                           150 ml                                               Catalyst: Phosphomolybdic acid                                                                         1.0 g                                                ______________________________________                                    

Desired compound:

Glucosyloxypropyl methacrylate (HPMA-Glc)

Yield: 15.6 g (43%)

Infrared absorption spectrum analysis (liquid film method, cm⁻¹):

FIG. 5 shows the IR spectrum of the above compound. Major peaks were asfollows. 3400 (broad absorption due to O--H stretching) 2940 (absorptiondue to C--H stretching) 1710 (absorption due to C═O, carbonyl group)1640 (absorption due to C═C, double bond) 1450 (absorption due todeformation vibrations of CH₂, CH₃ and the like) 1050 (broad absorptionindicated by a peak in a shape peculiar to sugar residue)

¹ H-NMR: δ ppm (in D₂ O): 6.1, 5.6: CH₂ ═; 4.9: α-anomer hydrogen;4.2-4.5: --OCH₂ --; 3.2-4.2: sugar skeleton; 1.9: CH₃ (methacryl group);1.3: CH₃ (propylene).

    ______________________________________                                        Elementary analysis                                                                  C            H      O                                                  ______________________________________                                        Found    49.6%          7.3%   43.1%                                          Calcd.   51.0%          7.2%   41.8%                                          ______________________________________                                    

Example 7

Starting compounds:

    ______________________________________                                        Methyl glucoside        19.4   g                                              2-Hydroxyethyl acrylate 120    ml                                             Catalyst: Phosphomolybdic acid                                                                        1.0    g                                              ______________________________________                                    

Desired compound:

Glucosyloxy ethyl acrylate (HEA-Glc)

Yield: 22.5 g (81%)

Infrared absorption spectrum analysis (liquid film method, cm⁻¹):

FIG. 6 shows the IR spectrum of the foregoing compound. Major peaks wereas follows. 3400 (broad absorption due to O--H stretching) 2940(absorption due to C--H stretching) 1710 (absorption due to C═O,carbonyl group) 1630 (absorption due to C═C, double bond) 1450(absorption due to deformation vibrations of CH₂ and the like) 1050absorption indicated by a peak in a shape peculiar to sugar residue)

¹ H-NMR: δ ppm (in D₂ O): 5.6-6.8: CH₂ ═CH--; 4.9: α-anomer hydrogen ;4.2-4.5: --OCH₂ --; 3.2-4.2: sugar skeleton.

    ______________________________________                                        Elementary analysis                                                                  C            H      O                                                  ______________________________________                                        Found    47.1%          6.5%   46.4%                                          Calcd.   47.5%          6.5%   46.0%                                          ______________________________________                                    

Example 8

Starting compounds:

    ______________________________________                                        Methyl glucoside        19.4   g                                              2-Hydroxyethyl acrylate 140    ml                                             Catalyst: Phosphomolybdic acid                                                                        1.0    g                                              ______________________________________                                    

Desired compound:

Glucosyloxy propyl acrylate (HPA-Glc)

Yield: 14.0 g (48%)

Infrared absorption spectrum analysis (liquid film method, cm⁻¹): 3400(broad absorption due to O--H stretching) 2950 (absorption due to C--Hstretching) 1710 (absorption due to C═O, carbonyl group) 1630(absorption due to C═C, double bond) 1450 (absorption due to deformationvibrations of CH₂, CH₃ and the like) 1050 (broad absorption indicated bya peak in a shape peculiar to sugar residue)

¹ H-NMR: δ ppm (in D₂ O): 5.6-6.8: CH₂ ═CH--; 4.9: α-anomer hydrogen;4.2-4.5: --OCH₂ --; 3.2-4.2: sugar skeleton; 1.3: CH₃.

    ______________________________________                                        Elementary analysis                                                                  C            H      O                                                  ______________________________________                                        Found    48.9%          7.0%   44.1%                                          Calcd.   49.3%          6.9%   43.8%                                          ______________________________________                                    

Example 9

Starting compounds:

    ______________________________________                                        Methyl glucoside        19.4   g                                              Diethylene glycol methacrylate                                                                        180    ml                                             Catalyst: Phosphomolybdic acid                                                                        1.0    g                                              ______________________________________                                    

Desired compound:

Glucosyloxy ethoxyethyl methacrylate (HEEMA-Glc)

Yield: 22.5 g (67%)

Infrared absorption spectrum analysis (liquid film method, cm⁻¹): 3400(broad absorption due to O--H stretching) 2940 (absorption due to C--Hstretching) 1710 (absorption due to C═O, carbonyl group) 1640(absorption due to C═C, double bond) 1450 (absorption due to deformationvibrations of CH₂, CH₃ and the like) 1050 (broad absorption indicated bya peak in a shape peculiar to sugar residue)

¹ H-NMR: δ ppm (in D₂ O): 6.1, 5.6: CH₂ ═; 4.9: α-anomer hydrogen;3.2-4.5: --OCH₂ --, sugar skeleton; 1.9: CH₃.

    ______________________________________                                        Elementary analysis                                                                  C            H      O                                                  ______________________________________                                        Found    49.7%          7.3%   43.0%                                          Calcd.   50.0%          7.2%   42.8%                                          ______________________________________                                    

Example 10

Starting compounds:

    ______________________________________                                        Methyl β-D-galactoside                                                                           19.4   g                                              Diethylene glycol methacrylate                                                                        180    ml                                             Catalyst: Phosphomolybdic acid                                                                        1.0    g                                              ______________________________________                                    

Desired compound:

Galactosyloxy ethoxyethyl methacrylate (HEEMA-Gal)

Yield: 24.2 (72%)

Infrared absorption spectrum analysis (liquid film method, cm⁻¹): 3400(broad absorption due to O--H stretching) 2940 (absorption due to C--Hstretching) 1710 (absorption due to C═O, carbonyl group) 1640(absorption due to C═C, double bond) 1450 (absorption due to deformationvibrations of CH₂, CH₃ and the like) 1050 (broad absorption indicated bya peak in a shape peculiar to sugar residue)

¹ H-NMR: δ ppm (in D₂ O): 6.1, 5.6: CH₂ ═; 4.9: α-anomer hydrogen;3.2-4.5: --OCH₂ --, sugar skeleton; 1.9: CH₃.

    ______________________________________                                        Elementary analysis                                                                  C            H      O                                                  ______________________________________                                        Found    49.6%          7.3%   43.1%                                          Calcd.   50.0%          7.2%   42.8%                                          ______________________________________                                    

Example 11

Starting compounds:

    ______________________________________                                        Methyl glucoside        19.4   g                                              Diethylene glycol acrylate                                                                            160    ml                                             Catalyst: Phosphomolybdic acid                                                                        1.0    g                                              ______________________________________                                    

Desired compound:

Glucosyloxy ethoxyethyl acrylate (HEEA-Glc)

Yield: 21.3 g (66%)

Infrared absorption spectrum analysis (liquid film method, cm⁻¹): 3400(broad absorption due to O--H stretching) 2940 (absorption due to C--Hstretching) 1710 (absorption due to C═O, carbonyl group) 1630(absorption due to C═C, double bond) 1450 (absorption due to deformationvibrations of CH₂ and the like) 1050 (broad absorption indicated by apeak in a shape peculiar to sugar residue)

¹ H-NMR: δ ppm (in D₂ O): 5.6-6.8: CH₂═CH--; 4.9: β-anomer hydrogen;3.4-4.5: --OCH₂ --, sugar skeleton; 1.9: CH₃.

    ______________________________________                                        Elementary analysis                                                                  C            H      O                                                  ______________________________________                                        Found    47.8%          7.0%   45.2%                                          Calcd.   48.4%          6.9%   44.7%                                          ______________________________________                                    

EXAMPLE 12

A 2.0 g quantity of methyl D-maltotrioside was suspended in 15 ml ofdiethylene glycol methacrylate. To the suspension were added 0.1 g ofbutylhydroxytoluene and 0.2 g of phosphomolybdic acid, and the mixturewas stirred well and gradually heated. After heating to a temperature of70° to 80° C., the mixture was further stirred for about 2.5 hours whilemaintaining the same temperature and was neutralized with 2N sodiumhydroxide. To the reaction mixture was added 30 ml of ethyl acetate andthe resulting mixture was extracted with water, followed byconcentration of the aqueous layer under reduced pressure. The obtainedoily product was subjected to silica gel chromatography (eluent,chloroform:methanol=4:1 to 1:1). A fraction (R_(f) =0.2) of the reactionmixture was concentrated, giving 1.28 g of maltotriosyloxyethylmethacrylate (HEEMA-Glc3) as an oily product (yield 49%).

The analysis of the obtained compound showed the following results.

Silica gel TLC: 1 spot

Silica gel plate; product of Merck % Co., Inc., 60F254

Eluent, chloroform:methanol=4:1

Infrared absorption spectrum analysis (liquid film method, cm⁻¹); 3400(broad absorption due to O--H stretching) 2940 (absorption due to C--Hstretching) 1710 (absorption due to C═O, carbonyl group) 1640(absorption due to C═C, double bond) 1450 (absorption due to deformationvibrations of CH₂, CH₃ and the like) 1050 (broad absorption indicated bya peak in a shape peculiar to sugar residue)

¹ H-NMR: δ ppm (in D₂ O): 6.1, 5.6 (CH₂ ═) 5.2 (α-anomer hydrogen)3.2-4.5 (--OCH₂ --, sugar skeleton) 1.9 (CH₃).

    ______________________________________                                        Elementary analysis                                                                  C            H      O                                                  ______________________________________                                        Found    47.2%          6.7%   46.1%                                          Calcd.   47.3%          6.7%   46.0%                                          ______________________________________                                    

EXAMPLES 13 TO 14

The desired compounds were prepared in the same manner as in Example 3with the exception of using the following starting compounds, catalystsand polymerization inhibitors.

EXAMPLE 13

Starting compounds:

    ______________________________________                                        Methyl D-maltoside       3.6   g                                              2-Hydroxyethyl methacrylate                                                                            20    ml                                             Catalyst: Phosphomolybdic acid                                                                         0.1   g                                              Polymerization inhibitor:                                                                              0.3   g                                              Hydroquinone monomethyl ether                                                 ______________________________________                                    

Desired compound:

Maltosyloxyethyl methacrylate (HEMA-Mal)

Yield: 1.8 g (40%)

Infrared absorption spectrum analysis (liquid film method, cm⁻¹)

3400 (broad absorption due to O--H stretching)

2940 (absorption due to C--H stretching)

1710 (absorption due to C═O, carbonyl group)

1640 (absorption due to C═C, double bond)

1450 (absorption due to deformation vibrations of CH₂, CH₃ and the like)

1050 (broad absorption indicated by a peak in a shape peculiar to sugarresidue)

¹ H-NMR: δ ppm (in D₂ O): 6.1, 5.6: CH₂ ═; 4.9: α-anomer hydrogen;3.2-4.5: --OCH₂ --, sugar skeleton; 1.9: CH₃.

    ______________________________________                                        Elementary analysis                                                                  C            H      O                                                  ______________________________________                                        Found    47.0%          6.7%   46.3%                                          Calcd.   47.6%          6.7%   45.8%                                          ______________________________________                                    

EXAMPLE 14

Starting compounds:

    ______________________________________                                        Methyl β-D-lactoside                                                                              3.6   g                                              2-Hydroxyethyl methacrylate                                                                            20    ml                                             Catalyst: Phosphomolybdic acid                                                                         0.1   g                                              Polymerization inhibitor:                                                                              0.3   g                                              Hydroquinone monomethyl ether                                                 ______________________________________                                    

Desired compound:

Lactosyloxy ethyl methacrylate (HEMA-Lac)

Yield: 1.5 g (33%)

Infrared absorption spectrum analysis (liquid film method, cm⁻¹):

3400 (broad absorption due to O--H stretching)

2940 (absorption due to C--H stretching)

1710 (absorption due to C═O, carbonyl group)

1640 (absorption due to C═C, double bond)

1450 (absorption due to deformation vibrations of CH₂, CH₃ and the like)

1050 (broad absorption indicated by a peak in a shape peculiar to sugarresidue)

¹ H-NMR: δ ppm (in D₂ O): 6.1, 5.6: CH₂ ═; 4.9: α-anomer hydrogen;3.2-4.5: --OCH₂ --, sugar skeleton; 1.9: CH₃.

    ______________________________________                                        Elementary analysis                                                                  C            H      O                                                  ______________________________________                                        Found    47.0%          6.8%   46.2%                                          Calcd.   47.6%          6.7%   45.8%                                          ______________________________________                                    

EXAMPLE 15

Ninety grams of dextrose was suspended in 650 ml of 2-hydroxyetylmethacrylate. To the suspension were added 1.0 g of hydroquinonemonomethyl ether and 0.5 g of p-toluenesulfonic acid, and the mixturewas heated while blowing the air into the mixture. After heating toabout 110° C., the mixture was stirred for 2 hours while maintaining thesame temperature and was cooled, followed by neutralization with sodiumbicarbonate. The obtained reaction mixture was concentrated underreduced pressure and purified by silica gel chromatography (eluent,chloroform: methanol=1:0 to 1:1, gradient elution), giving 110 g ofHEMA-Glc as the desired product (yield 75%). The obtained compound wasidentical in the analysis data with the compound produced in Example 1.

EXAMPLES 16 TO 19

HEMA-Glc was obtained as the desired product by the same procedure as inExample 15 with the exception of using the catalysts in specific amountsand the polymerization inhibitors as shown in Table 1. The resultingproducts were identical in the analysis data with the compound obtainedin Example 1.

                  TABLE 1                                                         ______________________________________                                        Catalyst          Polymerization                                                                             Yield                                          Kind        Amount (g)                                                                              inhibitor    (g)  (%)                                   ______________________________________                                        Ex. 16                                                                              ClSO.sub.3 H                                                                            0.1       MMHQ       112  77                                  Ex. 17                                                                              DSA       0.5       MMHQ       100  68                                  Ex. 18                                                                              ABS       0.5       MMHQ        93  64                                  Ex. 19                                                                              FeCl.sub.3                                                                              1.0       BHT         99  68                                  ______________________________________                                         ClSO.sub.3 H; chlorosulfonic acid                                             DSA; laurylsulfuric acid                                                      ABS; laurylbenzenesulfonic acid                                               FeCl.sub.3 ; ferric chloride                                                  MMHQ; hydroquinone monomethyl ether                                           BHT; butylhydroxytoluene                                                 

EXAMPLES 20 TO 22

The same procedure as in Example 15 was repeated with the exception ofusing the following starting compounds and catalysts, giving the desiredcompounds.

EXAMPLE 20

Starting compounds:

    ______________________________________                                        Methyl β-D-galactoside                                                                           90     g                                              2-Hydroxyethyl methacrylate                                                                           650    ml                                             Catalyst: p-Toluenesulfonic acid                                                                      0.2    g                                              Polymerization inhibitor:                                                                             1.0    g                                              Butylhydroxytoluene                                                           ______________________________________                                    

Desired compound: HEMA-Gal

Yield: 115 g (79%)

The obtained product was identical in the analysis data with thecompound prepared in Example 3.

EXAMPLE 21

Starting compounds:

    ______________________________________                                        Dextrose                80     g                                              2-Hydroxyethyl acrylate 600    ml                                             Catalyst: p-Toluenesulfonic acid                                                                      0.2    g                                              Polymerization inhibitor:                                                                             1.0    g                                              Butylhydroxytoluene                                                           ______________________________________                                    

Desired compound: HEA-Glc

Yield: 110 g (79%)

The obtained product was identical in the analysis data with thecompounds prepared in Example 7.

EXAMPLE 22

Starting compounds:

    ______________________________________                                        Dextrose                80     g                                              Diethylene glycol methacrylate                                                                        880    ml                                             Catalyst: Sulfuric acid 0.2    g                                              ______________________________________                                    

Desired compound: HEEMA-Glc

Yield: 120 g (71%)

The obtained product was identical in the analysis data with thecompound produced in Example 9.

EXAMPLE 23

A 90 g quantity of dextrose was suspended in 650 ml of 2-hydroxyethylmethacrylate. Hydroquinone monomethyl ether (1.0 g) was added to thesuspension and the mixture was heated while blowing the air into themixture. After heating the mixture to about 110° C., 50 ml of2-hydroxyethyl methacrylate having dissolved therein 0.2 g ofp-toluenesulfonic acid was added while maintaining the same temperature.The obtained mixture was stirred for 2 hours and cooled. The resultingmixture was treated and purified in the same manner as in Example 15,giving 115 g of HEMA-Glc as the desired product (yield 79%). Theobtained compound was identical in the analysis data with the compoundprepared in Example 1.

EXAMPLE 24

The same procedure as in Example 23 was repeated with the exception ofusing 0.2 g of sulfuric acid in place of p-toluenesulfonic acid, giving118 g of HEMA-Glc (yield 81%). The obtained compound was identical inthe analysis data with the compound prepared in Example 1.

EXAMPLES 25 TO 32

The desired compounds were produced in the same manner as in Example 23using the following starting compounds and catalysts.

EXAMPLE 25

Starting compounds:

    ______________________________________                                        Galactose               90     g                                              2-Hydroxyethyl methacrylate                                                                           650    ml                                             Catalyst: Sulfuric acid 0.1    g                                              ______________________________________                                    

Desired compound: HEMA-Gal

Yield: 113 g (77%)

The obtained product was identical in the analysis data with thecompound produced in Example 3.

EXAMPLE 26

Starting compounds:

    ______________________________________                                        Mannose                 90     g                                              2-Hydroxyethyl methacrylate                                                                           650    ml                                             Catalyst: p-Toluenesulfonic acid                                                                      0.2    g                                              ______________________________________                                    

Desired compound: HEMA-Man

Yield: 102 g (70%)

The obtained product was identical in the analysis data with thecompound prepared in Example 4.

EXAMPLE 27

Starting compounds:

    ______________________________________                                        Xylose                  75     g                                              2-Hydroxyethyl methacrylate                                                                           650    ml                                             Catalyst: Sulfuric acid 0.2    g                                              ______________________________________                                    

Desired compound: HEMA-Xyl

Yield: 97 g (74%)

The obtained product was identical in the analysis data with thecompound prepared in Example 5.

EXAMPLE 28

Starting compounds:

    ______________________________________                                        Dextrose                80     g                                              2-Hydroxypropyl methacrylate                                                                          720    ml                                             Catalyst: Sulfuric acid 0.2    g                                              Polymerization inhibitor:                                                                             1.0    g                                              Butylhydroxytoluene                                                           ______________________________________                                    

Desired compound: HPMA-Glc

Yield: 104 g (68%)

The obtained product was identical in the analysis data with thecompound prepared in Example 6.

EXAMPLE 29

Starting compounds:

    ______________________________________                                        Galactose               80     g                                              2-Hydroxyethyl acrylate 600    ml                                             Catalyst: p-Toluenesulfonic acid                                                                      0.2    g                                              ______________________________________                                    

Desired compound: HEA-Gal

Yield: 114 g (82%)

The obtained product was identical in the analysis data with thecompound produced in Example 2.

EXAMPLE 30

Starting compounds:

    ______________________________________                                        Dextrose                 80     g                                             2-Hydroxypropyl acrylate 720    ml                                            Catalyst: p-Toluenesulfonic acid                                                                       0.2    g                                             ______________________________________                                    

Desired compound: HPA-Glc

Yield: 94 g (64%)

The obtained product was identical in the analysis data with thecompound produced in Example 8.

EXAMPLE 31

Starting compounds:

    ______________________________________                                        Galactose                80     g                                             Diethylene glycol methacrylate                                                                         880    ml                                            Catalyst: Sulfuric acid  0.2    g                                             ______________________________________                                    

Desired compound: HEEMA-Gal

Yield: 121 g (72%)

The obtained product was identical in the analysis data with thecompound prepared in Example 10.

EXAMPLE 32

Starting compounds:

    ______________________________________                                        Dextrose                 80     g                                             Diethylene glycol methacrylate                                                                         180    ml                                            Catalyst: p-Toluenesulfonic acid                                                                       0.2    g                                             ______________________________________                                    

Desired compound: HEEA-Glc

Yield: 117 g (73%)

The obtained product was identical in the analysis data with thecompound prepared in Example 11.

EXAMPLE 33

A 3.4 g quantity of maltose was suspended in 20 ml of 2-hydroxyethylmethacrylate. To the suspension was added 0.5 g of hydroquinonemonomethyl ether and the mixture obtained was heated while blowing theair into the mixture. After heating the mixture to about 110° C., 1.0 mlof 2-hydroxyethyl methacrylate having dissolved therein 0.01 g ofp-toluenesulfonic acid was added while maintaining the same temperature.The resulting mixture was stirred for 2 hours and cooled. The obtainedreaction mixture was then treated and purified in the same manner as inExample 15, giving 1.5 g of HEMA-Mal as the desired compound (yield33%). The obtained product was identical in the analysis data with thecompound prepared in Example 13.

EXAMPLE 34

The same procedure as in Example 34 was repeated with the exception ofusing lactose in place of maltose, giving 1.2 g of HEMA-Lac as thedesired compound (yield 26%). The obtained product was identical in theanalysis data with the compound produced in Example 14.

Given below are Examples 35 to 86 illustrating the preparation ofglycoside derivative-containing polymers.

EXAMPLE 35

Ten grams of glucosyloxyethyl methacrylate (HEMA-Glc) was dissolved in70 ml of distilled water. To the solution was added 40 mg of ammoniumpersulfate (APS), and the mixture was reacted with stirring at 50° C.for 12 hours in a nitrogen stream. After completion of the reaction, thereaction mixture was poured into 1 l of acetone, and the precipitatedwhile crystals were collected by filtration, washed with acetone anddried under reduced pressure. The obtained white precipitate wasdissolved in 100 l of distilled water and the solution was poured into 1l of acetone. The precipitate was collected by filtration and driedunder reduced pressure, giving 9.5 g of poly (glucosyloxyethylmethacrylate) as a white powder (yield 95%).

Infrared absorption spectrum analysis (liquid film method, cm⁻¹):

3400 (broad peak due to O--H, hydroxyl group of sugar residue)

2940 (C--H)

1720 (C═O, carbonyl methacrylate)

1260 (broad peak)

1050 (broad peak peculiar to sugar residue)

¹³ C--NMR: δppm (DMSO-D₆):

FIG. 7 shows the ¹³ C-NMR spectrum of the above compound. ##STR13## C₁ :98 (α-anomer) 103 (β-anomer) C₂, C₃, C₄, C₅, C₆, C₅ ' and C₆ ': 61-76(ten-odd sharp peaks), C₁ ': 45, C₂ ': 54, C₃ ': 17, 19, C₄ ': 178, 179,

FIG. 8 shows the ¹ H-NMR spectrum of the above compound.

EXAMPLE 36

A 10 g quantity of galactosyloxyethyl methacrylate (HEMA-Gal) wasdissolved in 70 ml of DMSO. To the solution was added 25 mg of AIBN, andthe mixture was reacted with stirring at 65° C. for 12 hours in anitrogen stream. After completion of the reaction, the polymer wasrecovered by precipitation with acetone in the same manner as in Example35, purified by reprecipitation and dried under vacuum, giving 8.9 g ofpoly (galactosyloxy ethyl methacrylate) as a white powder (yield 89%).

Infrared absorption spectrum analysis (liquid film method, cm⁻¹):

The obtained product showed a spectrum similar to that obtained inExample 35.

¹³ C-NMR: δ ppm (DMSO-D₆): ##STR14## C₁ : 98 (α-anomer) 103 (β-anomer)C₂, C₃, C₄, C₅, C₆, C₅ ' and C₆ ': 61-76 (ten-odd sharp peaks) C₁ ': 45,C₂ ': 54, C₃ ': 17, 19, C₄ ': 178, 179

EXAMPLES 37 TO 48

Homopolymers were obtained in the same manner as in Example 35 with theexception of using the monomers, solvents for polymerization (distilledwater) in specified amounts (g), polymerization initiator (ammoniumpersulfate) in specified amounts (mg) and the reaction time (hour), asshown below in Table 2.

                  TABLE 2                                                         ______________________________________                                                    Amount Amount                                                                 of     of in-          Yield                                      Monomer       water    itiator  Time (g)  (%)                                 ______________________________________                                        Ex. 37                                                                              HEA-Gal     70       40     12   9.6  96                                Ex. 38                                                                              HEEMA-Glc3  60       30     12   9.5  95                                Ex. 39                                                                              HEMA-Man    70       40     10   9.7  97                                Ex. 40                                                                              HEMA-Xyl    90       40     10   9.4  94                                Ex. 41                                                                              HEMA-Mal    70       35     10   9.2  92                                Ex 42 HEMA-Lac    70       35     10   9.2  92                                Ex. 43                                                                              HPMA-Glc    70       40     10   9.8  98                                Ex. 44                                                                              HEA-Glc     70       40     10   9.7  97                                Ex. 45                                                                              HPA-Glc     70       40     10   9.7  97                                Ex. 46                                                                              HEEMA-Glc   70       35     10   9.0  90                                Ex. 47                                                                              HEEMA-Gal   70       35     10   8.9  89                                Ex. 48                                                                              HEEA-Glc    70       40     10   9.1  91                                ______________________________________                                    

Table 3 below shows the intrinsic viscosity (in DMSO, 25° C.) of thehomopolymers obtained in Examples 35 to 48 and the results of elementaryanalysis thereof.

                  TABLE 3                                                         ______________________________________                                                Intrinsic                                                                             Elementary analysis (Calcd.)                                  Example No.                                                                             viscosity C         H      O                                        ______________________________________                                        35        1.56      49.0      7.5    43.5                                                         (49.3)    (6.9)  (43.8)                                   36        1.82      46.7      8.3    45.0                                                         (49.3)    (6.9)  (43.8)                                   37        1.50      46.2      6.5    47.3                                                         (47.5)    (6.5)  (46.0)                                   38        2.50      46.0      6.8    47.2                                                         (47.3)    (6.7)  (46.0)                                   39        1.80      48.5      7.1    44.4                                                         (49.3)    (6.9)  (43.8)                                   40        1.75      49.1      7.1    43.8                                                         (50.3)    (6.9)  (42.7)                                   41        2.33      46.3      6.8    46.9                                                         (47.6)    (6.7)  (45.8)                                   42        2.12      47.3      6.9    45.8                                                         (47.6)    (6.7)  (45.8)                                   43        1.55      50.8      7.4    41.8                                                         (51.0)    (7.2)  (41.8)                                   44        1.62      46.9      6.5    46.6                                                         (47.5)    (6.5)  (46.0)                                   45        1.65      49.2      6.9    43.9                                                         (49.3)    (6.9)  (43.8)                                   46        2.08      49.6      7.3    43.1                                                         (50.0)    (7.2)  (42.8)                                   47        2.03      49.5      7.3    43.2                                                         (50.0)    (7.2)  (42.8)                                   48        1.88      48.0      6.9    45.1                                                         (48.4)    (6.9)  (44.7)                                   ______________________________________                                    

The homopolymers obtained in Examples 35 to 48 are soluble in water,DMSO and DMF and insoluble in other organic solvents.

EXAMPLE 49

A 7.0 g quantity of glucosyloxyethyl methacrylate (HEMA-Glc) and 13.0 gof methyl methacrylate were dissolved in 70 ml of DMSO. A 25 mg quantityof AIBN was added to the obtained solution and the mixture was reactedwith stirring at 65° C. for 10 hours in a nitrogen stream. Aftercompletion of the reaction, the highly viscous reaction mixture wasdiluted with 70 ml of DMSO and poured into 2 l of acetone to give asolution from which a copolymer was precipitated. The precipitate waspurified by reprecipitation, giving 18.8 g of a white powder ofcopolymer (yield 94%).

The polymer swelled in water, greatly swelled in acetone, dissolved inacetone/water mixtures (9/1 and 8/2) and dissolved in DMSO.

Infrared absorption spectrum analysis reveals that peaks were found at1440 (--COOCH₃) and at 980, 830 and 740 (all due to methyl methacrylate)in addition to the same peaks as observed in the analysis of thehomopolymer obtained in Example 35.

When a film formed from this copolymer was immersed in water, the filmheld water in an amount corresponding to 58.1% of the weight of thecopolymer and changed to a transparent film outstanding in strength andflexibility.

EXAMPLE 50

A 12.0 g quantity of glucosyloxyethyl methacrylate (HEMA-Glc), 8.0 g ofmethyl methacrylate, 40 ml of ethyl cellosolve, 16 ml of isopropanol and14 ml of water were mixed together. To the mixture was added 30 mg ofAIBN and the obtained mixture was reacted with stirring at 65° C. for 8hours in a nitrogen stream. After completion of the reaction, thereaction mixture was purified in the same manner as in Example 49,giving 17.9 g of a copolymer as a white powder (yield 89.5%).

The thus obtained copolymer greatly swelled in water, slightly swelledin acetone, swelled in an acetone/water (9/1) mixture, dissolved in anacetone/water (8/2) mixture and dissolved in DMSO.

The copolymer showed the same infrared absorption spectrum as observedin the analysis of the copolymer obtained in Example 49.

When immersed in water, this copolymer changed to a soft gel containingwater in an amount corresponding to 227% of the weight of the copolymer.

EXAMPLE 51

A 12.0 g quantity of galactosyloxyethyl acrylate (HEA-Gal), 8.0 g ofstyrene, 40 ml of ethyl cellosolve, 16 ml of isopropanol and 14 ml ofwater were mixed together. The mixture was treated by the same procedureas in Example 50, giving 15.2 g of a copolymer as a white powder (yield76%).

The polymer swelled in water, did not swelled in acetone, greatlyswelled in an acetone/water (9/1) mixture, greatly swelled in anacetone/water (8/2) mixture and dissolved in DMSO and in ethylcellosolve.

The polymer showed absorptions at 1610, 1500, 1450 and 750 all due tothe benzene ring in addition to the same infrared absorptions asobserved in the analysis of the homopolymer obtained in Example 48.

EXAMPLE 52

In 80 ml of DMSO were dissolved 10 g of galactosyloxyethyl methacrylate(HEMA-Gal) and 10 g of acrylonitrile. Thirty millgrams of AIBM was addedto the obtained solution and the mixture was reacted with stirring at70° C. for 12 hours in a nitrogen stream, giving a pale yellow,transparent viscous liquid. The obtained liquid was diluted with 80 mlof DMSO and the diluted liquid was poured into 2 l of acetone to give asolution from which a copolymer was prepared. The precipitate waspurified by reprecipitation, giving 17.8 g of a white powder ofcopolymer (yield 89%).

The polymer swelled in water, swelled in acetone, greatly swelled in anacetone/water (8/2) mixture, dissolved in DMSO and was insoluble inethyl cellosolve.

The polymer showed sharp peaks at 2170 (--C N) and 1430 (--CH₂ --CN) inaddition to the same infrared absorptions as observed in the analysis ofthe homopolymer obtained in Example 48.

EXAMPLES 53 TO 88

Copolymers were prepared by the same reactions as conducted in Examples49 to 52 except under the conditions as shown below in Table 4. All theobtained copolymers were soluble in DMSO and DMF, and those obtained inExamples 57, 58, 60 and 83 to 86 were soluble also in water.

In Table 4 below, Note 1) indicates a solvent mixture of 40 ml of ethylcellosolve, 16 ml of isopropanol and 14 ml of water.

                                      TABLE 4                                     __________________________________________________________________________    Example                                                                            Monomers used                                                                             Solvent                                                                              Initiator                                                                             Temperature                                                                          Time                                                                             Yield                               No.  Kind     (g)                                                                              (Amount, ml)                                                                         (Amount, mg)                                                                          (°C.)                                                                         (hr)                                                                             (g)                                                                              (%)                              __________________________________________________________________________    53   HEMA-Glc 8.0                                                                              Note 1)                                                                              AIBN    65     8  17.5                                                                             87.5                                  Styrene  12.0                                                                             (70)   (30)                                                  54   HEMA-Glc 12.0                                                                             DMSO   AIBN    65     8  15.8                                                                             79.0                                  Styrene  8.0                                                                              (70)   (30)                                                  55   HEMA-Glc 8.0                                                                              DMSO   AIBN    65     8  17.9                                                                             89.5                                  Acrylonitrile                                                                          12.0                                                                             (80)   (30)                                                  56   HEMA-Glc 12.0                                                                             DMSO   AIBN    65     8  18.2                                                                             91.0                                  Acrylonitrile                                                                          8.0                                                                              (80)   (30)                                                  57   HEMA-Glc 8.0                                                                              DMSO   AIBN    70     10 16.2                                                                             81.0                                  Acrylamide                                                                             12.0                                                                             (70)   (35)                                                  58   HEMA-Glc 12.0                                                                             DMSO   AIBN    70     10 17.5                                                                             87.5                                  Acrylamide                                                                             8.0                                                                              (70)   (35)                                                  59   HEMA-Glc 10.0                                                                             DMSO   AIBN    65     10 16.5                                                                             82.5                                  2-Hydroxyethyl                                                                         10.0                                                                             (70)   (30)                                                       methacrylate                                                             60   HEMA-Glc 15.0                                                                             Water  APS     50     10 15.2                                                                             76.0                                  Methacrylic acid                                                                       5.0                                                                              (70)   (40)                                                  61   HEMA-Gal 8.0                                                                              DMSO   AIBN    65     8  18.2                                                                             91.0                                  Methyl   12.0                                                                             (70)   (30)                                                       methacrylate                                                             62   HEMA-Gal 12.0                                                                             DMSO   AIBN    65     8  17.9                                                                             89.5                                  Methyl   8.0                                                                              (70)   (30)                                                       methacrylate                                                             63   HEMA-Gal 12.0                                                                             Note 1)                                                                              AIBN    65     8  16.5                                                                             82.5                                  Styrene  8.0                                                                              (70)   (30)                                                  64   HEMA-Gal 10.0                                                                             DMSO   AIBN    65     8  15.8                                                                             79.0                                  2-Hydroxyethyl                                                                         10.0                                                                             (70)   (30)                                                       methacrylate                                                             65   HEMA-Man 10.0                                                                             DMSO   AIBN    65     8  18.0                                                                             90.0                                  Methyl   10.0                                                                             (70)   (30)                                                       methacrylate                                                             66   HEMA-Xyl 10.0                                                                             DMSO   AIBN    65     8  17.8                                                                             89.0                                  Methyl   10.0                                                                             (80)   (30)                                                       methacrylate                                                             67   HEMA-Mal 10.0                                                                             DMSO   AIBN    65     8  18.5                                                                             92.5                                  Acrylonitrile                                                                          10.0                                                                             (80)   (30)                                                  68   HEMA-Lac 10.0                                                                             DMSO   AIBN    65     8  18.3                                                                             91.5                                  Acrylonitrile                                                                          10.0                                                                             (80)   (30)                                                  69   HPMA-Glc 10.0                                                                             DMSO   AIBN    65     8  17.6                                                                             88.0                                  Methyl   10.0                                                                             (70)   (30)                                                       methacrylate                                                             70   HPMA-Glc 10.0                                                                             DMSO   AIBN    65     8  18.8                                                                             94.0                                  Acrylonitrile                                                                          10.0                                                                             (70)   (30)                                                  71   HEA-Glc  10.0                                                                             DMSO   AIBN    65     8  18.5                                                                             92.5                                  Methyl   10.0                                                                             (70)   (30)                                                       methacrylate                                                             72   HEA-Glc  10.0                                                                             DMSO   AIBN    65     8  18.9                                                                             94.5                                  Acrylonitrile                                                                          10.0                                                                             (70)   (30)                                                  73   HEA-Gal  10.0                                                                             DMSO   AIBN    65     8  18.2                                                                             91.0                                  Methyl   10.0                                                                             (70)   (30)                                                       methacrylate                                                             74   HEA-Gal  10.0                                                                             DMSO   AIBN    65     8  17.9                                                                             89.5                                  Acrylonitrile                                                                          10.0                                                                             (70)   (30)                                                  75   HPA-Glc  10.0                                                                             DMSO   AIBN    65     8  18.1                                                                             90.5                                  Methyl   10.0                                                                             (70)   (30)                                                       methacrylate                                                             76   HEEMA-Glc                                                                              10.0                                                                             DMSO   AIBN    65     8  18.3                                                                             91.5                                  Methyl   10.0                                                                             (80)   (30)                                                       methacrylate                                                             77   HEEMA-Glc                                                                              15.0                                                                             Note 1)                                                                              AIBN    65     8  16.7                                                                             83.5                                  Styrene  5.0                                                                              (70)   (30)                                                  78   HEEMA-Glc                                                                              10.0                                                                             DMSO   AIBN    65     8  18.0                                                                             90.0                                  Acrylonitrile                                                                          10.0                                                                             (80)   (30)                                                  79   HEEMA-Gal                                                                              10.0                                                                             DMSO   AIBN    65     8  17.8                                                                             89.0                                  Methyl   10.0                                                                             (80)   (30)                                                       methacrylate                                                             80   HEEMA-Gal                                                                              10.0                                                                             DMSO   AIBN    65     8  18.2                                                                             91.0                                  Acrylonitrile                                                                          10.0                                                                             (80)   (30)                                                  81   HEEA-Glc 10.0                                                                             DMSO   AIBN    65     8  18.2                                                                             91.0                                  Methyl   10.0                                                                             (80)   (30)                                                       methacrylate                                                             82   HEEA-Glc 10.0                                                                             DMSO   AIBN    65     8  18.7                                                                             93.5                                  Acrylonitrile                                                                          10.0                                                                             (80)   (30)                                                  83   HEMA-Glc 10.0                                                                             Water  APS     50     10 19.2                                                                             96.0                                  HEMA-Gal 10.0                                                                             (80)   (40)                                                  84   HEMA-Glc 10.0                                                                             Water  APS     50     10 18.9                                                                             94.5                                  HEA-Glc  10.0                                                                             (80)   (40)                                                  85   HEMA-Glc 10.0                                                                             Water  APS     50     10 19.3                                                                             96.5                                  HEMA-Xyl 10.0                                                                             (80)   (40)                                                  86   HEMA-Glc 10.0                                                                             Water  APS     50     10 19.1                                                                             95.5                                  HEEMA-Glc                                                                              10.0                                                                             (80)   (40)                                                  87   HEEMA-Glc3                                                                             7.0                                                                              DMSO   AIBN    65     10 17.6                                                                             88.0                                  Methyl   13.0                                                                             (70)   (25)                                                       methacrylate                                                             88   HEEMA-Glc3                                                                             12.0                                                                             DMSO   AIBN    65     10 16.8                                                                             84.0                                  Methyl   8.0                                                                              (70)   (25)                                                       methacrylate                                                             __________________________________________________________________________

Table 5 below shows the intrinsic viscosity (in DMSO, at 25° C.), ratioof the copolymerized monomers and the results of elementary analysis,with respect to the copolymers obtained above.

The ratio of the copolymerized monomers was determined by the "sugaranalysis", "elementary analysis" and "other methods" as described below.

Sugar analysis

A 50 mg quantity of the copolymer was dispersed or dissolved in 10 ml ofa 2N aqueous solution of hydrochloric acid to undergo hydrolysis at 95°to 100° C. for 6 hours. After completion of the reaction, theprecipitate was filtered off and the sugar in the filtrate wasquantitatively determined according to the phenolsulfuric acid method.

Elementary analysis

In respect of copolymers containing a nitrogen-containing monomer, theratio of the copolymerized monomers was determined from the nitrogencontent obtained by elementary analysis, whereas as tostyrene-containing copolymers, the ratio thereof was determined from thecarbon content obtained by elementary analysis.

Other methods

Example 83: The ratio of constituent monomers was determined from theresults of quantitative determination of sugar in the foregoing sugaranalysis, quantitative determination of sugar by liquid chromatographyand quantitative determination of glucose thereby.

Liquid chromatography:

The same filtrate as obtained after hydrolysis in the sugar analysis wassubjected to liquid chromatography under the following conditions:

Column: TSKgel Amide-80

Eluent: a 75/25 mixture of acetonitrile/water

Flow rate: 1.0 ml/min

Detector: differential refractive index detector (RI)

Determination of glucose:

The same filtrate as obtained after hydrolysis in the sugar analysis wassubjected to colorimetric determination with use of a kit fordetermination of glucose (trade name: Glucose B-test kit, manufacturedby Wako Pure Chemicals, Inc.).

Example 84: The ratio of the copolymerized monomers was determined fromthe results of sugar analysis and elementary analysis and was confirmedby ¹ H-NMR.

¹ H-NMR:

Conducted in heavy water and determined from the following peak. 0.8-1.3ppm (broad peak due to CH₃ group)

Example 85: Determined from the results of the quantitative analysis ofthe sugar constituents by liquid chromatography.

Example 86: The ratio of the copolymerized monomers was determined fromthe results of sugar analysis and elementary analysis and was confirmedby ¹³ C-NMR.

¹³ C-NMR: Conducted in heavy water and determined from the followingpeaks. 66.1-63.7 ppm (several sharp peaks due to CH₂ in ethylene moiety)

(Note: In Table 5, the term "copolymerization ratio" means the ratio ofthe copolymerized monomers.)

                                      TABLE 5                                     __________________________________________________________________________    Constituent monomers                                                                             Method for deter-                                                                            Elementary                                  Example       Ratio                                                                              mining copolymeri-                                                                      Intrinsic                                                                          analysis (Calcd.)                           No.  Kind     (mol %)                                                                            zation ratio                                                                            viscosity                                                                          C   H  N                                    __________________________________________________________________________    49   HEMA-Glc 14.4 Sugar analysis                                                                          1.93 54.0                                                                              6.7                                                                              0.0                                       Methyl   85.6                (54.1)                                                                            (6.6)                                                                            (0.0)                                     methacrylate                                                             50   HEMA-Glc 34.6 Sugar analysis                                                                          0.52 51.4                                                                              6.7                                                                              0.0                                       Methyl   65.4                (51.4)                                                                            (6.8)                                                                            (0.0)                                     methacrylate                                                             51   HEA-Gal  41.1 Elementary                                                                              0.48 55.0                                                                              6.7                                                                              0.0                                       Styrene  58.6 analysis       (55.0)                                                                            (6.7)                                                                            (0.0)                                52   HEMA-Gal 16.0 Elementary                                                                              2.08 52.1                                                                              6.7                                                                              3.9                                       Acrylonitrile                                                                          84.0 analysis       (52.1)                                                                            (6.7)                                                                            (3.9)                                53   HEMA-Glc 19.1 Elementary                                                                              0.60 64.3                                                                              7.2                                                                              0.0                                       Styrene  80.9 analysis       (64.3)                                                                            (7.2)                                                                            (0.0)                                54   HEMA-Glc 38.2 Elementary                                                                              0.80 56.6                                                                              7.0                                                                              0.0                                       Styrene  61.8 analysis       (56.6)                                                                            (7.0)                                                                            (0.0)                                55   HEMA-Glc 10.3 Elementary                                                                              2.10 53.5                                                                              6.6                                                                              5.9                                       Acrylonitrile                                                                          89.7 analysis       (53.5)                                                                            (6.6)                                                                            (5.9)                                56   HEMA-Glc 21.5 Elementary                                                                              2.50 51.3                                                                              6.8                                                                              2.8                                       Acrylonitrile                                                                          78.5 analysis       (51.3)                                                                            (6.8)                                                                            (2.8)                                57   HEMA-Glc 16.3 Elementary                                                                              2.72 49.6                                                                              6.9                                                                              4.6                                       Acrylamide                                                                             83.7 analysis       (49.6)                                                                            (6.9)                                                                            (4.6)                                58   HEMA-Glc 30.2 Elemantary                                                                              2.90 49.5                                                                              6.9                                                                              2.4                                       Acrylamide                                                                             69.8 analysis       (49.5)                                                                            (6.9)                                                                            (2.4)                                59   HEMA-Glc 35.3 Sugar analysis                                                                          3.43 50.8                                                                              7.2                                                                              0.0                                       2-Hydroxyethyl                                                                         64.7                (50.9)                                                                            (7.1)                                                                            (0.0)                                     methacrylate                                                             60   HEMA-Glc 50.4 Sugar analysis                                                                          3.21 49.2                                                                              6.8                                                                              0.0                                       Methacrylic acid                                                                       49.6                (49.9)                                                                            (6.7)                                                                            (0.0)                                61   HEMA-Gal 18.4 Sugar analysis                                                                          1.85 53.0                                                                              6.7                                                                              0.0                                       Methyl   81.6                (53.3)                                                                            (6.7)                                                                            (0.0)                                     methacrylate                                                             62   HEMA-Gal 33.4 Sugar analysis                                                                          1.96 51.1                                                                              6.8                                                                              0.0                                       Methyl   66.6                (51.5)                                                                            (6.8)                                                                            (0.0)                                     methacrylate                                                             63   HEMA-Gal 39.8 Elementary                                                                              0.73 56.2                                                                              7.0                                                                              0.0                                       Styrene  60.2 analysis       (56.2)                                                                            (7.0)                                                                            (0.0)                                64   HEMA-Gal 32.6 Sugar analysis                                                                          3.32 50.8                                                                              7.2                                                                              0.0                                       2-Hydroxyethyl                                                                         67.4                (51.1)                                                                            (7.1)                                                                            (0.0)                                     methacrylate                                                             65   HEMA-Man 25.0 Sugar analysis                                                                          1.94 52.0                                                                              6.7                                                                              0.0                                       Methyl   75.0                (52.3)                                                                            (6.7)                                                                            (0.0)                                     methacrylate                                                             66   HEMA-Xyl 27.6 Sugar analysis                                                                          1.16 53.0                                                                              6.8                                                                              0.0                                       Methyl   72.4                (53.3)                                                                            (6.7)                                                                            (0.0)                                     methacrylate                                                             67   HEMA-Mal 10.1 Elementary                                                                              3.31 49.8                                                                              6.6                                                                              2.9                                       Acrylonitrile                                                                          89.9 analysis       (49.8)                                                                            (6.6)                                                                            (2.9)                                68   HEMA-Lac 10.0 Elementary                                                                              3.29 49.8                                                                              6.6                                                                              2.9                                       Acrylonitrile                                                                          90.0 analysis       (49.8)                                                                            (6.6)                                                                            (2.9)                                69   HPMA-Glc 23.5 Sugar analysis                                                                          1.82 53.1                                                                              7.0                                                                              0.0                                       Methyl   76.5                (53.5)                                                                            (7.0)                                                                            (0.0)                                     methacrylate                                                             70   HPMA-Glc 14.6 Elementary                                                                              2.87 53.5                                                                              7.0                                                                              3.9                                       Acrylonitrile                                                                          85.4 analysis       (53.5)                                                                            (7.0)                                                                            (3.9)                                71   HEA-Glc  25.1 Sugar analysis                                                                          1.64 50.9                                                                              6.4                                                                              0.0                                       Methyl   74.9                (51.2)                                                                            (6.4)                                                                            (0.0)                                     methacrylate                                                             72   HEA-Glc  15.8 Elementary                                                                              2.75 50.8                                                                              6.4                                                                              4.3                                       Acrylonitrile                                                                          84.2 analysis       (50.8)                                                                            (6.4)                                                                            (4.3)                                73   HEA-Gal  26.1 Sugar analysis                                                                          1.77 50.7                                                                              6.5                                                                              0.0                                       Methyl   73.9                (51.1)                                                                            (6.4)                                                                            (0.0)                                     methacrylate                                                             74   HEA-Gal  16.0 Elementary                                                                              2.80 50.8                                                                              6.3                                                                              4.2                                       Acrylonitrile                                                                          84.0 analysis       (50.8)                                                                            (6.3)                                                                            (4.2)                                75   HPA-Glc  24.9 Sugar analysis                                                                          1.68 52.1                                                                              6.8                                                                              0.0                                       Methyl   75.1                (52.3)                                                                            (6.7)                                                                            (0.0)                                     methacrylate                                                             76   HEEMA-Glc                                                                              22.4 Sugar analysis                                                                          2.43 52.2                                                                              7.0                                                                              0.0                                       Methyl   77.6                (52.6)                                                                            (7.0)                                                                            (0.0)                                     methacrylate                                                             77   HEEMA-Glc                                                                              54.6 Elementary                                                                              2.58 53.1                                                                              7.2                                                                              0.0                                       Styrene  45.4 analysis       (53.1)                                                                            (7.2)                                                                            (0.0)                                78   HEEMA-Glc                                                                              13.5 Elementary                                                                              3.43 52.5                                                                              7.0                                                                              3.6                                       Acrylonitrile                                                                          86.5 analysis       (52.5)                                                                            (7.0)                                                                            (0.0)                                79   HEEMA-Gal                                                                              22.9 Sugar analysis                                                                          2.04 52.3                                                                              7.0                                                                              0.0                                       Methyl   77.1                (52.5)                                                                            (7.0)                                                                            (0.0)                                     methacrylate                                                             80   HEEMA-Gal                                                                              13.4 Elementary                                                                              4.02 52.5                                                                              7.0                                                                              3.7                                       Acrylonitrile                                                                          86.6 analysis       (52.5)                                                                            (7.0)                                                                            (3.7)                                81   HEEA-Glc 23.3 Sugar analysis                                                                          3.86 51.1                                                                              6.8                                                                              0.0                                       Methyl   76.7                (51.4)                                                                            (6.7)                                                                            (0.0)                                     methacrylate                                                             82   HEEA-Glc 13.9 Elementary                                                                              4.03 51.2                                                                              6.7                                                                              3.8                                       Acrylonitrile                                                                          86.1 analysis       (51.2)                                                                            (6.7)                                                                            (3.8)                                83   HEMA-Glc 50.2 Other method                                                                            1.96 49.2                                                                              6.9                                                                              0.0                                       HEMA-Gal 49.8                (49.3)                                                                            (6.9)                                                                            (0.0)                                84   HEMA-Glc 48.5 Other method                                                                            2.43 48.2                                                                              6.7                                                                              0.0                                       HEA-Glc  51.5                (48.4)                                                                            (6.7)                                                                            (0.0)                                85   HEMA-Glc 47.2 Other method                                                                            1.75 49.7                                                                              6.9                                                                              0.0                                       HEMA-Xyl 52.8                (49.8)                                                                            (6.9)                                                                            (0.0)                                86   HEMA-Glc 54.3 Other method                                                                            4.03 49.5                                                                              7.1                                                                              0.0                                       HEEMA-Glc                                                                              45.7                (49.7)                                                                            (7.1)                                                                            (0.0)                                87   HEEMA-Glc3                                                                              7.9 Sugar analysis                                                                          2.01 49.5                                                                              6.5                                                                              0.0                                       Methyl   92.1                (50.0)                                                                            (6.5)                                                                            (0.0)                                     methacrylate                                                             88   HEEMA-Glc3                                                                             19.4 Sugar analysis                                                                          0.75 47.5                                                                              6.6                                                                              0.0                                       Methyl   80.6                (48.1)                                                                            (6.5)                                                                            (0.0)                                     methacrylate                                                             __________________________________________________________________________

EXAMPLE 89

Six grams of glucosyloxyethyl methacrylate (HEMA-Glc), 4 g of methylmethacrylate and 10 g of methacrylic acid were dissolved in a solventmixture of 105 ml of isopropanol (IPA) and 35 ml of water. Thirtymilligrams of AIBN was added to the obtained solution and the mixturewas reacted with stirring at 65° C. for 8 hours in a nitrogen stream.After completion of the reaction, the reaction mixture was diluted with30 mg of IPA and the diluted mixture was poured into 2 l of hexane togive a solution from which a copolymer was precipitated. The precipitatewas purified by reprecipitation, giving 18.5 g of a white powder ofcopolymer (yield 92.5%). The intrinsic viscosity [η] of the obtainedpolymer was 0.82 (in DMF, 25° C.). The polymer was soluble in awater/IPA (9/1) mixture, a water/IPA/toluene (1/8/2) mixture, ethylcellosolve, DMSO and DMF.

EXAMPLE 90

Polystyrene beads (150 μm in diameter) were immersed in solutions of 2wt % of each of the polymers 1 to 8 as shown below in Table 6 in adioxane/water mixture (the ratio of dioxane to water was changedaccording to the solubility of the polymer). The superfluous solutionwas filtered off and the beads were dried at 100° C. and further vacuumdried at 80° C. for 10 hours, giving polystyrene beads coated with eachpolymer (film thickness: 2 to 3 μm).

Since the polymers 1 and 2 were soluble in water, p-toluenesulfonic acidwas added to the solution in an amount corresponding to 0.3% of theweight of the polymer and the obtained mixture was heated to 100° C. tocause the crosslinking of hydoxyl groups on the sugar residue beforecoating the beads. After the crosslinking, the reaction mixture wasimmersed in water to remove the catalyst.

A platelet-rich plasma collected by centrifuging the citrated blood of arabbit was adjusted to a final concentration to a hundred thousandcells/μl. At room temperature, the plasma was loaded into a Tefloncolumn containing the polystyrene beads coated with each polymer. Fromthe number of platelets measured before and after the loading, thepercentage of platelets adhering to the beads (percentage of adhesion ofplatelets, %) was determined. Table 6 shows the results.

                  TABLE 6                                                         ______________________________________                                        Specimen      Ratio of adhesion of platelets (%)                              ______________________________________                                        Uncoated      97.0                                                            Polymer-1 (Ex. 35)                                                                          8.2                                                             Polymer-2 (Ex. 36)                                                                          7.6                                                             Polymer-3 (Ex. 49)                                                                          12.3                                                            Polymer-4 (Ex. 50)                                                                          5.2                                                             Polymer-5 (Ex. 51)                                                                          7.5                                                             Polymer-6 (Ex. 38)                                                                          7.3                                                             Polymer-7 (Ex. 87)                                                                          10.8                                                            Polymer-8 (Ex. 88)                                                                          7.5                                                             ______________________________________                                    

Table 6 reveals that only a very small quantity of platelets remainedadhered to the surface of the material of the invention.

EXAMPLE 91

A suspension of platelets of a rabbit (3×10⁸ pieces/ml) having loadedtherein a fluorescent coloring matter Furo2-AM capable of bonding toCa²⁺ was poured into a Teflon column containing the polystyrene beadscoated with each of the polymers 1 to 8 by the same procedure as inExample 1. The concentration of Ca²⁺ in the platelets eluted out of theTeflon column was measured with use of a calcimeter. Table 2 below showsthe incremental amount of the concentration (nM) of Ca²⁺ before andafter charging the suspension into the column.

                  TABLE 7                                                         ______________________________________                                                    Incremental amount of Ca.sup.2+                                   Specimen    concentration (nM)                                                ______________________________________                                        Uncoated    420                                                               Polymer-1   130                                                               Polymer-2   125                                                               Polymer-3   158                                                               Polymer-4    93                                                               Polymer-5   112                                                               Polymer-6   108                                                               Polymer-7   144                                                               Polymer-8    90                                                               ______________________________________                                    

Table 7 shows that the platelets contacted with the material of theinvention are unlikely to become active and that the material of theinvention has a very high compatibility with blood.

EXAMPLES 92 TO 110

The polymers 1 to 8 of the invention used in Examples 90 and 91 and thepolymer-9 of the invention prepared in Example 89 were each admixed withthe additives as shown below in Table 8 in the listed amounts (byweight), giving the compositions of the invention having a solidscontent of 20%.

A silicone oligomer, i.e. a hydrolyzate of silicone, to be used as theadditives was prepared by adding dropwise 6.9 g of a 0.02N aqueoussolution of hydrochloric acid to 30 g ofγ-glycidoxypropyl-trimetoxysilane with stirring and allowing theresulting mixture to age by standing overnight.

COMPARISON EXAMPLES 1 TO 4

The following 2-HEMA-containing copolymer (polymer-10) was mixed withthe additives as shown in Table 8 in the listed amounts (by weight),giving a comparative composition having a solids content of 20%.

Synthesis of 2-HEMA-containing copolymer:

A 12 g quantity of 2-hydroxyethyl methacrylate and 8 g of methylmethacrylate were dissolved in a solvent mixture of 40 ml of ethylcellosolve, 16 ml of IPA and 40 ml of water. Thirty milligrams of AIBNwas added to the obtained solution and the mixture was reacted withstirring at 65° C. for 8 hours in a nitrogen stream. After completion ofthe reaction, the reaction mixture was diluted with 70 ml of IPA and thediluted mixture was poured into 2 l of hexane to give a solution fromwhich a copolymer was precipitated. The precipitate was purified byreprecipitation, giving 18.2 g of a white powder of copolymer (yield91%). This copolymer will be hereinafter referred to as "polymer-10".The intrinsic viscosity [η] of the polymer was 0.50 (in DMF, 25° C.).

The solvent used in Examples 1 to 4 was a mixture ofmethanol/IPA/water/DMF (=45/30/15/10, ratio by volume, ml). The solventused in the other Examples and Comparison Examples was a mixture ofmethanol/IPA/water/carbitol acetate (=45/30/15/10, ratio by volume, ml).

                                      TABLE 8                                     __________________________________________________________________________               Example                                                                       92 93 94 95 96 97 98 99 100                                                                              101                                                                              102                                                                              103                               __________________________________________________________________________    Polymer                                                                       No.        1  1  2  2  3  3  4  4  9  9  9  9                                 Amount     100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                               Sorbitol poly-glycidyl                                                                   70 70 70 70 20 20 20 20 20 20                                      ether                                                                         Methylated                               20 20                                melamine resin                                                                Silicone oligomer                                                             1,8-Diaza- 1  1  1  1  1  1  1  1  1  1                                       bicyclo(5,4,0)                                                                undecene-7                                                                    p-Toluene-                               1  1                                 sulfonic acid                                                                 Dodecylglucoside                                                                            10    10    10    10    10                                      Polyoxyethylene                                                               nonyl phenyl ether                                                            __________________________________________________________________________               Example              Comp. Example                                            104                                                                              105                                                                              106                                                                              107                                                                              108                                                                              109                                                                              110                                                                              1   2   3   4                                 __________________________________________________________________________    Polymer                                                                       No.        9  9  9  5  6  7  8  10  10  10  10                                Amount     100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100                                                                              100 100 100 100                               Sorbitol poly-glycidyl                                                                            20 70 20 20 20  20                                        ether                                                                         Methylated 20                           20  20                                melamine resin                                                                Silicone oligomer                                                                           40 40                                                           1,8-Diaza-    1.5                                                                              1.5                                                                              1  1  1  1  1   1                                         bicyclo(5,4,0)                                                                undecene-7                                                                    p-Toluene- 1                            1   1                                 sulfonic acid                                                                 Dodecylglucoside                                                              Polyoxyethylene                                                                          10    10 10 10 10 10     10      10                                nonyl phenyl                                                                  ether                                                                         __________________________________________________________________________

The additives listed in Table 8 are sorbitol polyglycidyl ether (tradename: DENACOL EX-614, product of Nagase Kasei Kogyo Co., Ltd.),methylated melamine resin (tade name: Sumimal M-55, product of SumitomoChemical Co., Ltd.) and 1,8-diazabicyclo(5,4,0)undecene-7 (product ofSAN-APPRO Ltd.).

The obtained composition was applied to a 2 mm-thick plate made of apolycarbonate (trade name: POLYCACE, product of Tsutsunaka PlasticIndustry Co., Ltd.) to a dry film thickness of 8 to 12 μm. The coatedplate was cured by heating at 120° C. for 1 hour.

The following tests were carried out using as a specimen the thusobtained polycarbonate plate coated with a non-fogging, drip-proof film.Table 9 shows the results.

Non-fogging and drip-proof properties:

The apparatus as illustrated in FIG. 9 was used to check the specimensfor the non-fogging and drip-proof properties. In FIG. 9, the referencecharacters designate: 1, a specimen; 2, a stirring rod (blade); 3,thermometer; 4, a cover; 5, heat-insulating vessel; 6, heater; 7, warmwater (40° C.); and 8, steam. The specimen was placed at the specifiedposition in the apparatus, and the time taken until the occurrence offogging on the specimen was measured. The degrees of non-fogging anddrip-proof properties were evaluated according to the followingcriteria.

A: One minute or longer. Very satisfactory in non-fogging property.

B: 30 to 60 seconds. Satisfactory in non-fogging property.

C: 10 to 30 seconds. Insufficient in non-fogging property.

D: Up to 10 seconds. Poor in non-fogging property.

Contact angle:

In a room at 25° C., the contact angle of the coating was measured whilepouring 1 ml of pure water over the specimen with capillaries. Specimenshaving a contact angle of up to 5° were indicated with the mark "A".

Surface hardness:

The specimen was rubbed with a mat of steel wool #0000 (load: 5 g/cm²),and the degree of scratching detected on the coating was evaluatedaccording to the following criteria.

A: No mar was detected on the specimen.

B: The specimen sustained 1 or 2 scratches but with no problem.

C: The specimen sustained 5 to 10 scratches but with no problem.

D: More than 10 scratches were detected on the specimen.

Water resistance:

The specimen was immersed in water at 25° C. for 12 hours, and theappearance of the coating was evaluated according to the followingcriteria.

A: No change.

B: The coating slightly swelled, but returned to the original statebefore immersion when left to stand.

C: The coating significantly swelled and did not return to the originalstate when left to stand.

D: The coating peeled from the specimen during the immersion in water.

The degree of fogging on the coating was evaluated according to the samecriteria as above.

Resistance to hot water:

The specimen was immersed in hot water at 80° C. for 30 minutes, and theappearance of the coating was evaluated according to the same criteriaas in the water resistance test.

The degree of fogging of the coating was evaluated according to the samecriteria as above.

    __________________________________________________________________________                Example                                                                       92 93 94 95 96 97 98 99 100                                                                              101                                                                              102                                                                              103                              __________________________________________________________________________    Non-fogging property                                                                      A  A  A  A  B  A  A  A  B  A  B  A                                Contact angle                                                                             A  A  A  A  38 A  35 A  37 A  41 A                                Surface hardness                                                                          B  B  B  B  B  B  B  B  B  B  A  A                                Water resistance                                                              Appearance  B  B  B  B  B  B  B  B  B  B  B  B                                Non-fogging property                                                                      A  A  A  A  B  A  A  A  B  A  B  A                                Resistance to hot water                                                       Appearance  B  B  B  B  B  B  B  B  B  B  B  B                                Non-fogging property                                                                      A  A  A  A  B  A  A  A  B  A  B  A                                __________________________________________________________________________                Example                Comp. Example                                          104                                                                              105                                                                              106 107                                                                              108                                                                              109 110                                                                              1  2   3  4                                __________________________________________________________________________    Non-fogging property                                                                      B  A  A   A  A  A   A  D  B   D  B                                Contact angle                                                                             A  30 A   A  A  A   A  51 A   55 A                                Surface hardness                                                                          A  A  A   B  B  B   B  C  C   C  C                                Water resistance                                                              Appearance  B  B  B   B  B  B   B  C  C   B  B                                Non-fogging property                                                                      A  A  A   A  A  A   A  D  D   D  D                                Resistance to hot water                                                       Appearance  B  B  B   B  B  B   B  C  C   B  B                                Non-fogging property                                                                      A  A  A   A  A  A   A  D  D   D  D                                __________________________________________________________________________

Table 9 reveals that the cured coatings formed from the composition ofthe invention are excellent in non-fogging and drip-proof properties,substantially free of reduction in non-fogging and drip-proof propertieseven when exposed to water or hot water, very satisfactory in resistanceto scratching, and well-balanced in the properties required ofnon-fogging and drip-proof coatings.

We claim:
 1. A glycoside derivative-containing polymer having at leastone of repeated units (I) represented by the formula ##STR15## whereinG--O-- is a saccharide residue having no protective group, R is ahydrogen atom or a methyl group, m is 1 or 2, n is an integer of 1 to 4,and l is an integer of 1 or more provided that l≦n.
 2. A polymeraccording to claim 1 which is a homopolymer having repeated units (I) ora copolymer having at least two different repeated units (I).
 3. Apolymer according to claim 2 which is a copolymer having repeated units(I) and repeated units copolymerizable therewith.
 4. A polymer accordingto claim 3 wherein the copolymerizable repeated units are olefin-typerepeated units.
 5. A polymer according to claim 4 wherein theolefin-type repeated units are those represented by the formula##STR16## wherein R², R³ and R⁴ are the same or different and eachrepresent a hydrogen atom or a methyl group, and R⁵ is a group ##STR17##(wherein R⁶ is a hydrogen atom, an alkyl group, a hydroxyalkyl group, acycloalkyl group, an aminoalkyl group, a dialkylaminoalkyl group, aglycidyl group, a tetrahydrofuranyl group, a benzyl group, a group--(CH₂ CH₂ O)_(a) CH₂ CH₂ OH (wherein a is an integer of 1 to 10), agroup ##STR18## (wherein R⁷ is a hydrogen atom or a lower alkyl group,provided that two groups R⁷ are the same or different), a cyano group, ahydroxy group, a group ##STR19## (wherein R⁸ is a lower alkyl group), aphenyl group which may have at least one substituent selected from thegroup consisting of chlorine atom, lower alkyl group, cyano group, aminogroup, hydroxy group and lower alkoxy group, a pyridyl group optionallysubstituted with a lower alkyl group, a 2-oxypyrrolyl group optionallysubstituted with an alkyl group, or a carbazole group.
 6. A polymeraccording to claim 3 wherein the copolymer has 1 to 99 mole % ofrepeated units (I) and 99 to 1 mole % of repeated units copolymerizabletherewith.
 7. A material compatible with blood which contains theglycoside derivative-containing polymer of claim
 1. 8. A non-foggingdrip-proof composition which contains the glycosidederivative-containing polymer of claim 1.